Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 568195 12 pageshttpdxdoiorg1011552013568195
Research ArticleSynthesis Characterization and Thermal and AntimicrobialActivities of Some Novel Organotin(IV) Purine Base Complexes
Reena Jain1 Rajeev Singh2 and N K Kaushik3
1 Department of Chemistry Hindu College University of Delhi Delhi 110007 India2Department of Chemistry Atma Ram Sanatan Dharma College University of Delhi Delhi 110007 India3 Department of Chemistry University of Delhi Delhi 110007 India
Correspondence should be addressed to Rajeev Singh rajeevarsdduacin
Received 27 May 2013 Revised 4 August 2013 Accepted 7 August 2013
Academic Editor Sulekh Chandra
Copyright copy 2013 Reena Jain et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited
A new series of organotin(IV) complexes with purine bases theophylline (HL1) and theobromine (L2) of the types R3Sn(L1)
R2Sn(L1)Cl R
3Sn(L2)Cl and R
2Sn(L2)Cl
2(R = C
6H5CH2ndash p-ClC
6H4CH2ndash) have been synthesized in anhydrous THF The
complexes were characterized by elemental analysis conductancemeasurements molecular weight determinations UV-vis IR 1H13CNMR andmass spectral studies Various kinetic and thermodynamic parameters of these complexes have also been determinedusing TGDTA technique The thermal decomposition techniques indicate the formation of SnO
2as a residue The results show
that the ligands act as bidentate forming a five-member chelate ring All the complexes are 1 1 metal-ligand complexes In order toassess their antimicrobial activity the ligands and their corresponding complexes have also been tested in vitro against bacteria (Ecoli S aureus and P pyocyanea) and fungi (Rhizopus oryzae and Aspergillus flavus) All the complexes exhibit remarkable activityand the results provide evidence that the studied complexes might indeed be a potential source of antimicrobial agents
1 Introduction
Organotin(IV) compounds are characterized by the presenceof at least one covalent carbon-organotin bond The com-pounds contain tin centres which are tetravalent and are clas-sified as mono- di- tri- and tetraorganotin(IV) dependingon the number of alkyl (R) or aryl (Ar) moieties Duringthe last 65 years the worldwide production of organotincompounds and their derivatives has increased considerablyowing to their activities as anticancer [1] antifouling [2ndash4] and bactericidal [5ndash9] fungicidal [7ndash13] antifertility [68 9] and antiviral agents [14] Since biocidal properties oforganotin(IV) compounds are dependent on both the organicgroup and the ligand attached to the tin [15 16] an interestingdevelopment is introducing ligands which are themselvesbioactive [15 17ndash19]
Compounds containing purine play a significant role inmany biological systems [20] where they exist in nucleicacids several vitamins coenzymes and antibiotics Theseprovide potential binding sites for metal ions and any
information on their coordinating properties is importantas a means of understanding the role of the metal ionin biological systems Theophylline (1 3-dimethylxanthine)and theobromine (3 7-dimethylxanthine) are referred toas purine bases and constitute an important class of anti-inflammatory agents [21]Theophylline has biological impor-tance as it is structurally related to nucleic acids components[22] and thus can be used as a drug for the treatmentof asthmatic bronchitis and chronic obstructive bronchitisunder a variety of brand names and as anticancer drugs
The interest inmetal complexes of theophylline and theo-bromine is stimulated by the fact that certain purine-metalcomplexes have been found to have therapeutic value asdiuretics [23] It is also important to study the mode ofbinding of the ligandwith themetal [24]Moreover the studyof the behavior of theophylline as a ligand can be useful forelucidating the metal and interligand interactions involvingthe purine bases of nucleic acids or their nucleosides as thetheophylline molecule can be considered as a model for thenucleoside guanosine In continuation of our previous work
2 Journal of Chemistry
N
N
C
C
O
O
NH
CH
N
5
43
2
16
78
9C
C
CH3
CH3
(a)
CH
N
N
C
C N
N
H5
43
2
16 7
89C
O
C
O
CH3
CH3
(b)
Figure 1 Structure of (a) theophylline and (b) theobromine ligands
here we present the synthesis mode of binding thermalstudies and antimicrobial properties of some organotin(IV)complexes with purine bases theophylline (Figure 1(a)) andtheobromine (Figure 1(b))
2 Experimental
21 PhysicalMeasurements All reagents used were AR gradeand the solvents were purified and dried by standard meth-ods and moisture was excluded from glass apparatus usingCaCl2drying tubes The elemental analysis was carried out
on an Elementar Analysensysteme GmbH Varion EL IIIGermany IR and far IR spectra were recorded on KBr andpolyethylene discs respectively using a Perkin Elmer Spec-trum 2000 FTIR spectrometer The 13C and 1HNMR spectrawere recorded in CDCl
3 respectively on a Bruker Spectro-
spin Advance 300 spectrometer Tetramethylsilane was usedas an internal reference for 1H NMR Varian Cary 100 UV-VIS spectrophotometer was used to record the electronicspectra of the compounds Conductance measurements werecarried out on Elico Conductivity Bridge (Type CM82T)and mass spectra were obtained using Jeol SX-102(FAB)mass spectrometer Thermal studies (TGDTA curves) wererecorded on a Rigaku Corporation Thermoflex PTC-10A instatic air at a heating rate of 10∘Cmin The Pt crucible wasused with alumina as the reference material Chlorine wasdetermined gravimetrically as silver chloride [25 26] Tinwasalso estimated gravimetrically as SnO
2[27]The antibacterial
activities were evaluated by the paper-disc plate method [28]and antifungal by agar plate technique [29]Molecularmassesof the complexes were determined by Cottrellrsquos method ofboiling point elevation [30]
22 Antimicrobial Activity
221 Antibacterial Activity For the evaluation of degreeof inhibitory effects on the growth of a wide spectrumof microorganisms antibacterial activity was performedagainst one Gram-positive (Staphylococcus aureus) and threeGram-negative (Escherichia coli Pseudomonas aeruginosaand Klebsiella pneumoniae) bacteria In order to compare theresults obtained the Imipenem was used as standard drug
Determination of the antibacterial activity was carried outby the paper-disc plate method [28] The compounds weredissolved in DMF at 500 and 1000 ppm concentrations TheWhatman no 1 papers with a diameter 5mm were soakedin these solutions These discs were placed on the appro-priate nutrient medium (05 peptone 015 yeast 015beef extract 035 sodium chloride and 013 KH
2PO4in
1000 cm3 distilled water which was autoclaved for 20min at15 psi before inoculation) previously seeded with organismsin Petri dishes and stored in an incubator at 28 plusmn 2∘C Theinhibition zone thus formed around each disc was measured(in mm) after 96 h
222 Antifungal Studies Bioefficacies of the synthesizedcompounds were checked in vitro The in vitro antifungalactivities of the ligands and their complexes were evalu-ated against two pathogenic fungi Rhizopus oryzae (causeszygomycosis) and Aspergillus flavus (causing aspergillosis oflungs) by the agar plate technique [29] In order to comparethe results obtained the Bavistin was used as standard drugThe compounds were directly mixed with the medium in001 and 01 (inmethanol) concentrationsThemediumwasthen poured into Petri plates and a small disc (07 cm) of thefungus culture was cut with a sterile cork borer and trans-ferred aseptically into the centre of a Petri dish containing themedium with a certain amount of the compound Suitablechecks were kept where the culture discs were grown underthe same conditions on PDA without the compound ThesePetri dishes were wrapped in polythene bags containing afew drops of alcohol and were placed in an incubator at 25plusmn 2∘C Controls were also run and three replicates were usedin each caseThe linear growth of the fungus was obtained bymeasuring the diameter of the fungal colony after four daysThe amount of growth inhibition in each of the replicate wascalculated by percentage inhibition = (119862minus119879)times100119862 where119862 is diameter of the fungus colony in the control plate after96 h and 119879 is diameter of the fungus colony in tested platesafter the same period
23 Preparation of Complexes (C6H5CH2)3SnCl (p-ClC
6H4sdot
CH2)3SnCl (C
6H5CH2)2SnCl2 and (p-ClC
6H5CH2)2SnCl2
were synthesized by the method given by Sisido et al[31] The organotin(IV) complexes of theophylline (HL1)
Journal of Chemistry 3
and theobromine (L2) were synthesized according to theprocedure reported by Bhatia et al [32]
A solution of theophylline (HL1 180 g 001mol) in 25mLTHF and 5 gNaOH was stirred for about 12 hrs at room tem-perature A solution of R
3SnCl or R
2SnCl2(001mol) in 25mL
THF was added to it and stirred for 4H at room temperatureThe contents were then filtered and the filtratewas reduced toone-fourth of its original volume The R
3SnL1 or R
2Sn(L1)Cl
complexes precipitated out on adding petroleum ether andwere recrystallised from acetone Theobromine complexeswere synthesized by simply adding a solution of R
3SnCl
or R2SnCl2(001mol) in 25mL THF to a suspension of
theobromine (L2 180 g 001mol) in 25mL THF and stirredfor 3 hours at room temperature The contents were filteredand volume was reduced to one-fourth of its original volumeThe R
3SnL2(Cl) or R
2Sn(L2)Cl
2complexes precipitated out
on addition of petroleum ether and were recrystallised fromacetone
3 Results and Discussion
Elemental analyses reveal that the complexes are of goodpurity and are yellow in colourThe complexes were found tobe soluble in acetonitrile THF DMSO acetone and CHCl
3
The complexes decomposed before melting The analyticaldata of the complexes along with their decomposition tem-perature is given in Table 1 From the analytical data it is clearthat organotin(IV) derivatives react with these ligands in1 1 molar proportions Conductancemeasurements for thesecomplexes in 10minus2M nitrobenzene solution are in the rangeof 012ndash040 ohmminus1 cm2molminus1 indicating that the complexesare nonelectrolytes
31 Infrared Studies In case of theophylline complexes theligand can chelate with the metal ion either through C(6)carbonyl and N(7) or through N(7) alone [24 32 33] In thepresent case the ](C=O) stretching frequency for free ligandwas observed at 1720 and 1660 cmminus1 On complexation thepeaks merged and appeared at ca 1700 cmminus1 However thisshift cannot be attributed to the interaction of carbonyl atC(6) with Sn(IV) since the electronic spectra of these com-plexes rules out this possibility Further the disappearanceof the band at 3200 cmminus1 due to ](NndashH) stretching in thecomplexes indicate that the ligand is linked to Sn(IV) throughthe deprotonation of N(7)
In case of free theobromine the ](C=O) stretching fre-quency appears at 1700 and 1665 cmminus1 and remains unalteredon complexation However the ](C=N) + ](C=C) stretchingfrequency is shifted from 1595 and 1550 cmminus1 in free theo-bromine to ca 1580 and 1530 cmminus1 in complexes indicatingthat the theobromine is linked to Sn(IV) through N(9) [34]
32 Electronic Spectra In the electronic spectra of theo-phylline and theobromine the band corresponding to 120587 rarr120587lowast transition of the carbonyl group at 270 nm (log120576 345) and
272 nm (log120576 35) respectively almost remained unperturbed
on complexation confirming the noninvolvement of the car-bonyl group of these ligands in complexation [32] Additionalpeaks at sim210 nm and sim250 nm corresponding to the phenylring of R moiety are observed in case of the UV spectrumof metal complexes In addition to this the ligand rarr metalcharge transfer band is observed in the region 320ndash340 nm(log 120576 sim 42) in the complexes
33 1H and 13C NMR Studies The 1H NMR data of thecomplexes are tabulated in Tables 2 and 3 The peaksundergo a slight downfield shift on complexation due tothe change in the electronic environment of the ligand Intheophylline the broad peak due to ndashNndashH (120575 104) disappearson complexation confirming that the complexation involvesthe replacement of hydrogen atom in ndashNndashHndash group In theo-bromine the peak corresponding to H-8 (120575 71) undergoessignificant downfield shift on complexation confirming theinvolvement ofN-9 in complexation [35] 13CNMRdata havebeen recorded for both the ligands and their correspondingorganotin(IV) complexes and these spectra also support theauthenticity of the proposed structures (C
6H5CH2)3Sn(L1)
13CNMR ppm theophyllinato C(2) 1558 C(3) 1495 C(5)1073 C(6) 1623 C(8) 1411 1-Me 284 3-Me 301 SnndashCH2 1787 aromatic 1418 1306 1288 1317 1279 1316
(C6H5CH2)3Sn(L2)Cl theobromine C(2) 1511 C(4) 1495
C(5) 1063 C(6) 1612 C(8) 1365 3-Me 291 7-Me 284 SnndashCH2 1956 aromatic 1428 1316 1298 1327 1289 1326
34 Mass Studies The fragmentation pattern of the com-plexes has been analysed on the basis of mass spectra TheRSn+ R+ and Sn+ ions dominate the mass spectra Thecarbonium ion R+ constitutes the base peak in the massspectra of all the complexes Schemes 1 and 2 representthe fragmentation pattern for theophylline and theobrominemoieties respectively in the organotin(IV) complexes
35 Thermal Studies Thermal studies have been carriedout for all the complexes The thermogravimetric (TG)studies reveal that only two of the prepared complexes(C6H5CH2)3Sn(L1) and (p-ClC
6H4CH2)3Sn(L1) undergo
decomposition in two steps whereas the rest undergo decom-position in three stepsThe first step (423ndash673K) involves theloss of R groups the second step corresponds to the loss ofchlorine atom(s) and the final step involves the formationof SnO
2 The mass loss data is given in Table 4 The DTA
curves reveal that all the decomposition steps except the stepcorresponding to the formation of SnO
2 are exothermic in
nature The last step corresponding to the formation of SnO2
is endothermic in natureThe order (119899) and activation energy (119864
119886) have been
elucidated for the various steps using Coats-Redfern [36]as well as Horowitz-Metzger [37] methods The values ofactivation energy and entropy of the reaction have beencalculated using both methods and found to be in closeagreement The order of reaction in each case is one ΔH(enthalpy of reaction) have been calculated using the TG [38]andDTA curves respectively [39 40]The kinetic parameters
4 Journal of Chemistry
Table1Ph
ysicalcharacteris
ticsa
ndanalyticaldataof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Empiric
alform
ula
MolW
tfoun
d(cal)
Decptemp(∘C)Λ119887(Cminus15
9times10minus2M)
Foun
d(cal)
SnCl
NC
H(C
6H5C
H2)
3Sn(L1)
C 28H
28N
4SnO
257076
(57124)
210
021
2019
(2077)
mdash96
1(98
0)5864(5887)
461
(494)
(p-C
lC6H
4CH
2)3Sn(L1)
C 28H
25N
4SnO
2Cl 3
67321
(67398)
170
019
1705
(176
1)1522(1569)
798(831
)4962(498
9)321
(373)
(C6H
5CH
2)2Sn(L1)C
lC 2
1H21N
4SnO
2Cl
51491
(51536)
240
024
2262(2303)
629
(684)
1038(1087)
4869(4894)
392
(410
)(p-C
lC6H
4CH
2)2Sn(L1)C
lC 2
1H21N
4SnO
2Cl
58261
(58385)
210
039
2006(2032)
1768
(1811)
926(959)
4299(4320)
302
(328)
(C6H
5CH
2)3Sn(L2)C
lC 2
8H29N
4SnO
2Cl
60681
(60750)
200
021
1916
(1953
)534
(580)
906(922)
5501(5535
)451
(481)
(p-C
lC6H
4CH
2)3Sn(L2)C
lC 2
8H26N
4SnO
2Cl 4
7092
9(71024)
150
029
1621(1671)
1931
(1985)
762(788)
4711
(4735)
329
(369)
(C6H
5CH
2)2Sn(L2)C
l 2C 2
1H22N
4SnO
2Cl 2
5510
0(55162)
220
030
2112
(215
1)1221(1278)
998(1015)
4554(4572)
365
(402)
(p-C
lC6H
4CH
2)2Sn(L2)C
l 2C 2
1H20N
4SnO
2Cl 4
6197
9(62011)
200
032
1869(19
14)
2219
(2273)
889
(903)
4021(40
67)
302
(325)
Journal of Chemistry 5
Table2
1 Hand
13CNMRdata(120575
ppm)o
ftheop
hylline
complexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theoph
yllin
emoiety
ArndashH
ndashCH
2ndashH-8
ndashCH
3atN-3
ndashCH
3atN-1
ndashNHndash
Theoph
yllin
e(HL1)
mdashmdash
75-76(d1H
)36-37(s3H)
32(s3H)
104ndash106(br2
H)
(C6H
5CH
2)3Sn(L1)
79ndash81(m
15H
)36-37(s6H)
77-78(d1H
)39-40(s3H)
33(s3H)
mdash1787
(p-C
lC6H
4CH
2)3Sn(L1)
80ndash
82(m
12H
)39(s6H)
76-77(d1H
)41-4
2(s3H)
34(s3H)
mdash2401
(C6H
5CH
2)2Sn(L1)C
l79
-80(m
10H
)38(s4H)
75-76(d1H
)40-41(s3
H)
33-34(s3H)
mdash1721
(p-C
lC6H
4CH
2)2Sn(L1)C
l80-81(m8H)
37-38(s4H)
77-78(d1H
)40(s3H)
34-35(s3H)
mdash2350
6 Journal of Chemistry
Table3
1 Hand
13CNMRdata(120575
ppm)o
ftheob
rominec
omplexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theobrom
inem
oiety
ArndashH
ndashCH
2ndashndashC
H3atN-3
ndashCH
3atN-2
H-8
ndashNHndash
Theobrom
ine(L2)
mdashmdash
33(s3H)
35(s3H)
71(s1H)
130ndash132(br1H
)(C
6H5C
H2)
3Sn(L2)C
l70
ndash74(m
15H
)38-39(s6H)
34-35(s3H)
36-37(s3H)
77(s1H)
132ndash134(br1H
)1956
(p-C
lC6H
4CH
2)3Sn(L2)C
l71ndash73(m
12H
)39(s6H)
33-34(s3H)
36-37(s3H)
76(s1H)
134ndash136(br1H
)2534
(C6H
5CH
2)2Sn(L2)C
l 270
ndash73(m
10H
)39-40(s4H)
34(s3H)
37(s3H)
75(s1H)
133ndash135(br1H
)1834
(p-C
lC6H
4CH
2)2Sn(L2)C
l 271ndash73(m
8H)
38(s4H)
33-34(s3H)
36(s3H)
78(s1H)
133ndash136(br1H
)2366
Journal of Chemistry 7
+
+
+
N
N
O
O
N
N
N
N
O
O
N
N+
Sn
Sn
Sn
N
N
O
O
N
N
R
R
RR
R
R
R
R
R
CH3
CH3 CH3
CH3
CH3
CH3
∙
∙
∙∙
∙
∙+
C7H7N4O2
+
me 17906
C7H7N4O2
+
me 17906
C6H5N3O2
+
me 15104
C7H7N4O2
∙
me 17906
minusHCN
minusHNC
NH
N
N
O
O
N
NH C
HN
C
O
O
NH
NH
N
N
N
N
NH
CH
CH CH
CH
N
N
H
(b)
(a)
O
CH3
CH3
CH3
CH3
+
+
+
+
C
N
N
minusCO
minusCO
+ C
C4H5N3
me 9505
C5H5N3O∙+
me 12304
N
N
O
O
N
N
N
N
O
O
N
N
+
+
+
+N
N
O
O
N
N
R
R
R
Sn
Sn
Sn R
R
R
R
R
R
CH3
CH3
CH3
CH3
CH3
CH3∙
∙
∙+
C7H7N4O2
+
me 17905
C7H7N4O2
∙
me 17905
Scheme 1 Fragmentation pattern for theophylline complexes
8 Journal of Chemistry
+
+
N
N
O
O
N
N
H
N
N
O
O
N
N
H
Cl
N
N
O
O
N
N
H
R R
R
Sn
Sn
R R
Cl R
CH3
CH3
CH3
CH3CH3
CH3
∙+
∙+
∙+
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 180
C5H8N3
me 109
C5H7N3
me 109
C4H5N2
me 82
C4H5Nme 67
N
N
O
O
N
N
H
NO
N
N
H
minusHCNminusHCN
minusHNCON
N
O
N
N
NCH
NCH
CHCHN
N
N
N
H
(b)
(a)
Nme 55
NHC
NH
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3CH3 ∙+
∙
∙
∙
∙+
∙+
N
N
N
minusCO
C6H7N3O∙+
me 137
O+
C+
+N
N
O
O
N
N
H
Sn
N
N
O
O
N
N
H
N
N
O
O
N
N
H
R R
RCl
Cl
Cl
R R
R
Sn
Sn
R R
R+
CH3
CH3
CH3
CH3
CH3
CH3∙+
∙+
∙+
C7H8N4O2
∙+
me 180
C7H8N4O2
me 180
Scheme 2 Fragmentation pattern for theobromine complexes
Journal of Chemistry 9
Table 4 Phenomenological data for the thermal decomposition of the complexes
Complex Step number TG plateaux (K) Mass loss Nature of lossObserved Calc
(C6H5CH2)3Sn(L1) I 483ndash673 460 4786 Loss of 3 benzyl groups
II 893ndash1003 720 7373 Formation of SnO2
(p-ClC6H4CH2)3Sn(L1) I 443ndash633 550 5580 Loss of 3 p-chlorobenzyl groups
II 873ndash973 750 7773 Formation of SnO2
(C6H5CH2)2Sn(L1)Cl
I 513ndash663 347 3536 Loss of 2 benzyl groupsII 703ndash773 420 4220 Loss of chlorine atomIII 893ndash973 694 7088 Formation of SnO2
(p-ClC6H4CH2)2Sn(L1)Cl
I 483ndash673 420 4294 Loss of 2 p-chlorobenzyl groupsII 723ndash793 470 4898 Loss of chlorine atomIII 873ndash973 735 7429 Formation of SnO2
(C6H5CH2)3Sn(L2)Cl
I 473ndash653 450 450 Loss of 3 benzyl groupsII 723ndash813 500 5080 Loss of chlorine atomIII 893ndash1003 740 7529 Formation of SnO2
(p-ClC6H4CH2)3Sn(L2)Cl
I 423ndash623 520 5295 Loss of 3 p-chlorobenzyl groupsII 703ndash753 570 5792 Loss of chlorine atomIII 873ndash973 780 7887 Formation of SnO2
(C6H5CH2)2Sn(L2)Cl2
I 493ndash653 320 3304 Loss of 2 benzyl groupsII 703ndash773 450 4582 Loss of chlorine atomsIII 873ndash993 710 7279 Formation of SnO2
(p-ClC6H4CH2)2Sn(L2)Cl2
I 473ndash653 400 4043 Loss of 2 p-chlorobenzyl groupsII 723ndash793 500 5180 Loss of chlorine atomsIII 873ndash973 750 7580 Formation of SnO2
for the thermal decomposition of the complexes are given inTable 5
On the basis of the above data it can be concludedthat the complexes with R = p-ClC
6H4CH2ndash have lower 119864
119886
value for step 1 as compared to the complexes with the samenumber of R groups but R = C
6H5CH2ndash because the electron
withdrawing effect of chlorine makes the RndashSn bond weakerand facilitates its thermal degradation Moreover tri(p-chlorobenzyl)tin derivative has the least activation energy forthe first step due to the greater steric hindrance
36 In Vitro Antibacterial Studies Themetal complexes werescreened versus Ecoli S aureus and P pyocyanea bacterialstrains using the respective ligands as the standard forcomparing the activities The samples were screened at threedifferent concentrations (25 50 and 100 120583g cmminus3) in DMFThe inhibitory power of the metal complexes was observedto be greater than that of the control The general orderof activity versus the three microorganisms is Saureus gt Ppyocyanea gt EcoliThe data is presented in Table 6
37 Antifungal Studies The results reported in Table 7 revealthat the organotin complexes with these ligands are muchmore active than the parent ligand against the same microor-ganisms With increase in concentration of the compoundsthere occurs increase in percentage of inhibition Higherconcentration proves inhibitory for fungal growth
Sn
Cl
ClCl
Cl
N
N
N
N
OH
OCH3
CH2
CH2
H3C
Figure 2
On the basis of spectral evidence Figure 2 representingcoordination has been prepared for one of the complexessynthesized
Conflict of Interests
The authors declare that they have no conflict of interests
10 Journal of Chemistry
Table5Kinetic
parametersfor
thetherm
aldecompo
sitionof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Step
number
TempK
Coats-
Redfernmetho
dHorow
itz-M
etzger
metho
dDTA
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
Thermaleffect
Δ119867
(Jgminus
1 )
(C6H
5CH
2)3Sn(L1)
1483ndash673
5109
941
5423
1046
Exo
minus2042
2893ndash1003
30635
3762
31017
3801
Endo
9446
(p-C
lC6H
4CH
2)3Sn(L1)
144
3ndash633
4030
850
4184
881
Exo
minus1746
2873ndash973
21882
2742
24323
2982
Endo
9326
(C6H
5CH
2)2Sn(L1)C
l1
513ndash663
6382
1200
6562
1233
Exo
minus2210
2703ndash773
1915
43206
2114
03326
Exo
minus8999
3893ndash973
36698
4541
35353
443
Endo
9042
(p-C
lC6H
4CH
2)2Sn(L1)C
l1
483ndash673
5470
1054
5523
1067
Exo
minus2169
2723ndash793
25529
3942
23849
3764
Exo
minus9246
3873ndash973
38294
4745
38048
4785
Endo
9291
(C6H
5CH
2)3Sn(L2)C
l1
473ndash653
3829
697
4046
795
Exo
minus3046
2723ndash813
8703
1206
9534
1383
Exo
minus5249
3893ndash1003
20812
2410
21731
2622
Endo
11112
(p-C
lC6H
4CH
2)3Sn(L2)C
l1
423ndash623
3191
620
3491
741
Exo
minus2962
2703ndash753
25529
4162
25021
4069
Exo
minus5162
3873ndash973
2393
33041
25095
3189
Endo
11342
(C6H
5CH
2)2Sn(L2)C
l 21
493ndash653
5744
1120
5855
1135
Exo
minus2994
2703ndash773
2815
74369
27433
4344
Exo
minus5160
3873ndash993
17632
2142
17857
2157
Endo
11021
(p-C
lC6H
4CH
2)2Sn(L2)C
l 21
473ndash653
5444
784
5645
826
Exo
minus3106
2723ndash793
1914
72947
19218
2971
Exo
minus5206
3873ndash973
23753
2901
24328
2999
Endo
11226
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
2 Journal of Chemistry
N
N
C
C
O
O
NH
CH
N
5
43
2
16
78
9C
C
CH3
CH3
(a)
CH
N
N
C
C N
N
H5
43
2
16 7
89C
O
C
O
CH3
CH3
(b)
Figure 1 Structure of (a) theophylline and (b) theobromine ligands
here we present the synthesis mode of binding thermalstudies and antimicrobial properties of some organotin(IV)complexes with purine bases theophylline (Figure 1(a)) andtheobromine (Figure 1(b))
2 Experimental
21 PhysicalMeasurements All reagents used were AR gradeand the solvents were purified and dried by standard meth-ods and moisture was excluded from glass apparatus usingCaCl2drying tubes The elemental analysis was carried out
on an Elementar Analysensysteme GmbH Varion EL IIIGermany IR and far IR spectra were recorded on KBr andpolyethylene discs respectively using a Perkin Elmer Spec-trum 2000 FTIR spectrometer The 13C and 1HNMR spectrawere recorded in CDCl
3 respectively on a Bruker Spectro-
spin Advance 300 spectrometer Tetramethylsilane was usedas an internal reference for 1H NMR Varian Cary 100 UV-VIS spectrophotometer was used to record the electronicspectra of the compounds Conductance measurements werecarried out on Elico Conductivity Bridge (Type CM82T)and mass spectra were obtained using Jeol SX-102(FAB)mass spectrometer Thermal studies (TGDTA curves) wererecorded on a Rigaku Corporation Thermoflex PTC-10A instatic air at a heating rate of 10∘Cmin The Pt crucible wasused with alumina as the reference material Chlorine wasdetermined gravimetrically as silver chloride [25 26] Tinwasalso estimated gravimetrically as SnO
2[27]The antibacterial
activities were evaluated by the paper-disc plate method [28]and antifungal by agar plate technique [29]Molecularmassesof the complexes were determined by Cottrellrsquos method ofboiling point elevation [30]
22 Antimicrobial Activity
221 Antibacterial Activity For the evaluation of degreeof inhibitory effects on the growth of a wide spectrumof microorganisms antibacterial activity was performedagainst one Gram-positive (Staphylococcus aureus) and threeGram-negative (Escherichia coli Pseudomonas aeruginosaand Klebsiella pneumoniae) bacteria In order to compare theresults obtained the Imipenem was used as standard drug
Determination of the antibacterial activity was carried outby the paper-disc plate method [28] The compounds weredissolved in DMF at 500 and 1000 ppm concentrations TheWhatman no 1 papers with a diameter 5mm were soakedin these solutions These discs were placed on the appro-priate nutrient medium (05 peptone 015 yeast 015beef extract 035 sodium chloride and 013 KH
2PO4in
1000 cm3 distilled water which was autoclaved for 20min at15 psi before inoculation) previously seeded with organismsin Petri dishes and stored in an incubator at 28 plusmn 2∘C Theinhibition zone thus formed around each disc was measured(in mm) after 96 h
222 Antifungal Studies Bioefficacies of the synthesizedcompounds were checked in vitro The in vitro antifungalactivities of the ligands and their complexes were evalu-ated against two pathogenic fungi Rhizopus oryzae (causeszygomycosis) and Aspergillus flavus (causing aspergillosis oflungs) by the agar plate technique [29] In order to comparethe results obtained the Bavistin was used as standard drugThe compounds were directly mixed with the medium in001 and 01 (inmethanol) concentrationsThemediumwasthen poured into Petri plates and a small disc (07 cm) of thefungus culture was cut with a sterile cork borer and trans-ferred aseptically into the centre of a Petri dish containing themedium with a certain amount of the compound Suitablechecks were kept where the culture discs were grown underthe same conditions on PDA without the compound ThesePetri dishes were wrapped in polythene bags containing afew drops of alcohol and were placed in an incubator at 25plusmn 2∘C Controls were also run and three replicates were usedin each caseThe linear growth of the fungus was obtained bymeasuring the diameter of the fungal colony after four daysThe amount of growth inhibition in each of the replicate wascalculated by percentage inhibition = (119862minus119879)times100119862 where119862 is diameter of the fungus colony in the control plate after96 h and 119879 is diameter of the fungus colony in tested platesafter the same period
23 Preparation of Complexes (C6H5CH2)3SnCl (p-ClC
6H4sdot
CH2)3SnCl (C
6H5CH2)2SnCl2 and (p-ClC
6H5CH2)2SnCl2
were synthesized by the method given by Sisido et al[31] The organotin(IV) complexes of theophylline (HL1)
Journal of Chemistry 3
and theobromine (L2) were synthesized according to theprocedure reported by Bhatia et al [32]
A solution of theophylline (HL1 180 g 001mol) in 25mLTHF and 5 gNaOH was stirred for about 12 hrs at room tem-perature A solution of R
3SnCl or R
2SnCl2(001mol) in 25mL
THF was added to it and stirred for 4H at room temperatureThe contents were then filtered and the filtratewas reduced toone-fourth of its original volume The R
3SnL1 or R
2Sn(L1)Cl
complexes precipitated out on adding petroleum ether andwere recrystallised from acetone Theobromine complexeswere synthesized by simply adding a solution of R
3SnCl
or R2SnCl2(001mol) in 25mL THF to a suspension of
theobromine (L2 180 g 001mol) in 25mL THF and stirredfor 3 hours at room temperature The contents were filteredand volume was reduced to one-fourth of its original volumeThe R
3SnL2(Cl) or R
2Sn(L2)Cl
2complexes precipitated out
on addition of petroleum ether and were recrystallised fromacetone
3 Results and Discussion
Elemental analyses reveal that the complexes are of goodpurity and are yellow in colourThe complexes were found tobe soluble in acetonitrile THF DMSO acetone and CHCl
3
The complexes decomposed before melting The analyticaldata of the complexes along with their decomposition tem-perature is given in Table 1 From the analytical data it is clearthat organotin(IV) derivatives react with these ligands in1 1 molar proportions Conductancemeasurements for thesecomplexes in 10minus2M nitrobenzene solution are in the rangeof 012ndash040 ohmminus1 cm2molminus1 indicating that the complexesare nonelectrolytes
31 Infrared Studies In case of theophylline complexes theligand can chelate with the metal ion either through C(6)carbonyl and N(7) or through N(7) alone [24 32 33] In thepresent case the ](C=O) stretching frequency for free ligandwas observed at 1720 and 1660 cmminus1 On complexation thepeaks merged and appeared at ca 1700 cmminus1 However thisshift cannot be attributed to the interaction of carbonyl atC(6) with Sn(IV) since the electronic spectra of these com-plexes rules out this possibility Further the disappearanceof the band at 3200 cmminus1 due to ](NndashH) stretching in thecomplexes indicate that the ligand is linked to Sn(IV) throughthe deprotonation of N(7)
In case of free theobromine the ](C=O) stretching fre-quency appears at 1700 and 1665 cmminus1 and remains unalteredon complexation However the ](C=N) + ](C=C) stretchingfrequency is shifted from 1595 and 1550 cmminus1 in free theo-bromine to ca 1580 and 1530 cmminus1 in complexes indicatingthat the theobromine is linked to Sn(IV) through N(9) [34]
32 Electronic Spectra In the electronic spectra of theo-phylline and theobromine the band corresponding to 120587 rarr120587lowast transition of the carbonyl group at 270 nm (log120576 345) and
272 nm (log120576 35) respectively almost remained unperturbed
on complexation confirming the noninvolvement of the car-bonyl group of these ligands in complexation [32] Additionalpeaks at sim210 nm and sim250 nm corresponding to the phenylring of R moiety are observed in case of the UV spectrumof metal complexes In addition to this the ligand rarr metalcharge transfer band is observed in the region 320ndash340 nm(log 120576 sim 42) in the complexes
33 1H and 13C NMR Studies The 1H NMR data of thecomplexes are tabulated in Tables 2 and 3 The peaksundergo a slight downfield shift on complexation due tothe change in the electronic environment of the ligand Intheophylline the broad peak due to ndashNndashH (120575 104) disappearson complexation confirming that the complexation involvesthe replacement of hydrogen atom in ndashNndashHndash group In theo-bromine the peak corresponding to H-8 (120575 71) undergoessignificant downfield shift on complexation confirming theinvolvement ofN-9 in complexation [35] 13CNMRdata havebeen recorded for both the ligands and their correspondingorganotin(IV) complexes and these spectra also support theauthenticity of the proposed structures (C
6H5CH2)3Sn(L1)
13CNMR ppm theophyllinato C(2) 1558 C(3) 1495 C(5)1073 C(6) 1623 C(8) 1411 1-Me 284 3-Me 301 SnndashCH2 1787 aromatic 1418 1306 1288 1317 1279 1316
(C6H5CH2)3Sn(L2)Cl theobromine C(2) 1511 C(4) 1495
C(5) 1063 C(6) 1612 C(8) 1365 3-Me 291 7-Me 284 SnndashCH2 1956 aromatic 1428 1316 1298 1327 1289 1326
34 Mass Studies The fragmentation pattern of the com-plexes has been analysed on the basis of mass spectra TheRSn+ R+ and Sn+ ions dominate the mass spectra Thecarbonium ion R+ constitutes the base peak in the massspectra of all the complexes Schemes 1 and 2 representthe fragmentation pattern for theophylline and theobrominemoieties respectively in the organotin(IV) complexes
35 Thermal Studies Thermal studies have been carriedout for all the complexes The thermogravimetric (TG)studies reveal that only two of the prepared complexes(C6H5CH2)3Sn(L1) and (p-ClC
6H4CH2)3Sn(L1) undergo
decomposition in two steps whereas the rest undergo decom-position in three stepsThe first step (423ndash673K) involves theloss of R groups the second step corresponds to the loss ofchlorine atom(s) and the final step involves the formationof SnO
2 The mass loss data is given in Table 4 The DTA
curves reveal that all the decomposition steps except the stepcorresponding to the formation of SnO
2 are exothermic in
nature The last step corresponding to the formation of SnO2
is endothermic in natureThe order (119899) and activation energy (119864
119886) have been
elucidated for the various steps using Coats-Redfern [36]as well as Horowitz-Metzger [37] methods The values ofactivation energy and entropy of the reaction have beencalculated using both methods and found to be in closeagreement The order of reaction in each case is one ΔH(enthalpy of reaction) have been calculated using the TG [38]andDTA curves respectively [39 40]The kinetic parameters
4 Journal of Chemistry
Table1Ph
ysicalcharacteris
ticsa
ndanalyticaldataof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Empiric
alform
ula
MolW
tfoun
d(cal)
Decptemp(∘C)Λ119887(Cminus15
9times10minus2M)
Foun
d(cal)
SnCl
NC
H(C
6H5C
H2)
3Sn(L1)
C 28H
28N
4SnO
257076
(57124)
210
021
2019
(2077)
mdash96
1(98
0)5864(5887)
461
(494)
(p-C
lC6H
4CH
2)3Sn(L1)
C 28H
25N
4SnO
2Cl 3
67321
(67398)
170
019
1705
(176
1)1522(1569)
798(831
)4962(498
9)321
(373)
(C6H
5CH
2)2Sn(L1)C
lC 2
1H21N
4SnO
2Cl
51491
(51536)
240
024
2262(2303)
629
(684)
1038(1087)
4869(4894)
392
(410
)(p-C
lC6H
4CH
2)2Sn(L1)C
lC 2
1H21N
4SnO
2Cl
58261
(58385)
210
039
2006(2032)
1768
(1811)
926(959)
4299(4320)
302
(328)
(C6H
5CH
2)3Sn(L2)C
lC 2
8H29N
4SnO
2Cl
60681
(60750)
200
021
1916
(1953
)534
(580)
906(922)
5501(5535
)451
(481)
(p-C
lC6H
4CH
2)3Sn(L2)C
lC 2
8H26N
4SnO
2Cl 4
7092
9(71024)
150
029
1621(1671)
1931
(1985)
762(788)
4711
(4735)
329
(369)
(C6H
5CH
2)2Sn(L2)C
l 2C 2
1H22N
4SnO
2Cl 2
5510
0(55162)
220
030
2112
(215
1)1221(1278)
998(1015)
4554(4572)
365
(402)
(p-C
lC6H
4CH
2)2Sn(L2)C
l 2C 2
1H20N
4SnO
2Cl 4
6197
9(62011)
200
032
1869(19
14)
2219
(2273)
889
(903)
4021(40
67)
302
(325)
Journal of Chemistry 5
Table2
1 Hand
13CNMRdata(120575
ppm)o
ftheop
hylline
complexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theoph
yllin
emoiety
ArndashH
ndashCH
2ndashH-8
ndashCH
3atN-3
ndashCH
3atN-1
ndashNHndash
Theoph
yllin
e(HL1)
mdashmdash
75-76(d1H
)36-37(s3H)
32(s3H)
104ndash106(br2
H)
(C6H
5CH
2)3Sn(L1)
79ndash81(m
15H
)36-37(s6H)
77-78(d1H
)39-40(s3H)
33(s3H)
mdash1787
(p-C
lC6H
4CH
2)3Sn(L1)
80ndash
82(m
12H
)39(s6H)
76-77(d1H
)41-4
2(s3H)
34(s3H)
mdash2401
(C6H
5CH
2)2Sn(L1)C
l79
-80(m
10H
)38(s4H)
75-76(d1H
)40-41(s3
H)
33-34(s3H)
mdash1721
(p-C
lC6H
4CH
2)2Sn(L1)C
l80-81(m8H)
37-38(s4H)
77-78(d1H
)40(s3H)
34-35(s3H)
mdash2350
6 Journal of Chemistry
Table3
1 Hand
13CNMRdata(120575
ppm)o
ftheob
rominec
omplexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theobrom
inem
oiety
ArndashH
ndashCH
2ndashndashC
H3atN-3
ndashCH
3atN-2
H-8
ndashNHndash
Theobrom
ine(L2)
mdashmdash
33(s3H)
35(s3H)
71(s1H)
130ndash132(br1H
)(C
6H5C
H2)
3Sn(L2)C
l70
ndash74(m
15H
)38-39(s6H)
34-35(s3H)
36-37(s3H)
77(s1H)
132ndash134(br1H
)1956
(p-C
lC6H
4CH
2)3Sn(L2)C
l71ndash73(m
12H
)39(s6H)
33-34(s3H)
36-37(s3H)
76(s1H)
134ndash136(br1H
)2534
(C6H
5CH
2)2Sn(L2)C
l 270
ndash73(m
10H
)39-40(s4H)
34(s3H)
37(s3H)
75(s1H)
133ndash135(br1H
)1834
(p-C
lC6H
4CH
2)2Sn(L2)C
l 271ndash73(m
8H)
38(s4H)
33-34(s3H)
36(s3H)
78(s1H)
133ndash136(br1H
)2366
Journal of Chemistry 7
+
+
+
N
N
O
O
N
N
N
N
O
O
N
N+
Sn
Sn
Sn
N
N
O
O
N
N
R
R
RR
R
R
R
R
R
CH3
CH3 CH3
CH3
CH3
CH3
∙
∙
∙∙
∙
∙+
C7H7N4O2
+
me 17906
C7H7N4O2
+
me 17906
C6H5N3O2
+
me 15104
C7H7N4O2
∙
me 17906
minusHCN
minusHNC
NH
N
N
O
O
N
NH C
HN
C
O
O
NH
NH
N
N
N
N
NH
CH
CH CH
CH
N
N
H
(b)
(a)
O
CH3
CH3
CH3
CH3
+
+
+
+
C
N
N
minusCO
minusCO
+ C
C4H5N3
me 9505
C5H5N3O∙+
me 12304
N
N
O
O
N
N
N
N
O
O
N
N
+
+
+
+N
N
O
O
N
N
R
R
R
Sn
Sn
Sn R
R
R
R
R
R
CH3
CH3
CH3
CH3
CH3
CH3∙
∙
∙+
C7H7N4O2
+
me 17905
C7H7N4O2
∙
me 17905
Scheme 1 Fragmentation pattern for theophylline complexes
8 Journal of Chemistry
+
+
N
N
O
O
N
N
H
N
N
O
O
N
N
H
Cl
N
N
O
O
N
N
H
R R
R
Sn
Sn
R R
Cl R
CH3
CH3
CH3
CH3CH3
CH3
∙+
∙+
∙+
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 180
C5H8N3
me 109
C5H7N3
me 109
C4H5N2
me 82
C4H5Nme 67
N
N
O
O
N
N
H
NO
N
N
H
minusHCNminusHCN
minusHNCON
N
O
N
N
NCH
NCH
CHCHN
N
N
N
H
(b)
(a)
Nme 55
NHC
NH
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3CH3 ∙+
∙
∙
∙
∙+
∙+
N
N
N
minusCO
C6H7N3O∙+
me 137
O+
C+
+N
N
O
O
N
N
H
Sn
N
N
O
O
N
N
H
N
N
O
O
N
N
H
R R
RCl
Cl
Cl
R R
R
Sn
Sn
R R
R+
CH3
CH3
CH3
CH3
CH3
CH3∙+
∙+
∙+
C7H8N4O2
∙+
me 180
C7H8N4O2
me 180
Scheme 2 Fragmentation pattern for theobromine complexes
Journal of Chemistry 9
Table 4 Phenomenological data for the thermal decomposition of the complexes
Complex Step number TG plateaux (K) Mass loss Nature of lossObserved Calc
(C6H5CH2)3Sn(L1) I 483ndash673 460 4786 Loss of 3 benzyl groups
II 893ndash1003 720 7373 Formation of SnO2
(p-ClC6H4CH2)3Sn(L1) I 443ndash633 550 5580 Loss of 3 p-chlorobenzyl groups
II 873ndash973 750 7773 Formation of SnO2
(C6H5CH2)2Sn(L1)Cl
I 513ndash663 347 3536 Loss of 2 benzyl groupsII 703ndash773 420 4220 Loss of chlorine atomIII 893ndash973 694 7088 Formation of SnO2
(p-ClC6H4CH2)2Sn(L1)Cl
I 483ndash673 420 4294 Loss of 2 p-chlorobenzyl groupsII 723ndash793 470 4898 Loss of chlorine atomIII 873ndash973 735 7429 Formation of SnO2
(C6H5CH2)3Sn(L2)Cl
I 473ndash653 450 450 Loss of 3 benzyl groupsII 723ndash813 500 5080 Loss of chlorine atomIII 893ndash1003 740 7529 Formation of SnO2
(p-ClC6H4CH2)3Sn(L2)Cl
I 423ndash623 520 5295 Loss of 3 p-chlorobenzyl groupsII 703ndash753 570 5792 Loss of chlorine atomIII 873ndash973 780 7887 Formation of SnO2
(C6H5CH2)2Sn(L2)Cl2
I 493ndash653 320 3304 Loss of 2 benzyl groupsII 703ndash773 450 4582 Loss of chlorine atomsIII 873ndash993 710 7279 Formation of SnO2
(p-ClC6H4CH2)2Sn(L2)Cl2
I 473ndash653 400 4043 Loss of 2 p-chlorobenzyl groupsII 723ndash793 500 5180 Loss of chlorine atomsIII 873ndash973 750 7580 Formation of SnO2
for the thermal decomposition of the complexes are given inTable 5
On the basis of the above data it can be concludedthat the complexes with R = p-ClC
6H4CH2ndash have lower 119864
119886
value for step 1 as compared to the complexes with the samenumber of R groups but R = C
6H5CH2ndash because the electron
withdrawing effect of chlorine makes the RndashSn bond weakerand facilitates its thermal degradation Moreover tri(p-chlorobenzyl)tin derivative has the least activation energy forthe first step due to the greater steric hindrance
36 In Vitro Antibacterial Studies Themetal complexes werescreened versus Ecoli S aureus and P pyocyanea bacterialstrains using the respective ligands as the standard forcomparing the activities The samples were screened at threedifferent concentrations (25 50 and 100 120583g cmminus3) in DMFThe inhibitory power of the metal complexes was observedto be greater than that of the control The general orderof activity versus the three microorganisms is Saureus gt Ppyocyanea gt EcoliThe data is presented in Table 6
37 Antifungal Studies The results reported in Table 7 revealthat the organotin complexes with these ligands are muchmore active than the parent ligand against the same microor-ganisms With increase in concentration of the compoundsthere occurs increase in percentage of inhibition Higherconcentration proves inhibitory for fungal growth
Sn
Cl
ClCl
Cl
N
N
N
N
OH
OCH3
CH2
CH2
H3C
Figure 2
On the basis of spectral evidence Figure 2 representingcoordination has been prepared for one of the complexessynthesized
Conflict of Interests
The authors declare that they have no conflict of interests
10 Journal of Chemistry
Table5Kinetic
parametersfor
thetherm
aldecompo
sitionof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Step
number
TempK
Coats-
Redfernmetho
dHorow
itz-M
etzger
metho
dDTA
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
Thermaleffect
Δ119867
(Jgminus
1 )
(C6H
5CH
2)3Sn(L1)
1483ndash673
5109
941
5423
1046
Exo
minus2042
2893ndash1003
30635
3762
31017
3801
Endo
9446
(p-C
lC6H
4CH
2)3Sn(L1)
144
3ndash633
4030
850
4184
881
Exo
minus1746
2873ndash973
21882
2742
24323
2982
Endo
9326
(C6H
5CH
2)2Sn(L1)C
l1
513ndash663
6382
1200
6562
1233
Exo
minus2210
2703ndash773
1915
43206
2114
03326
Exo
minus8999
3893ndash973
36698
4541
35353
443
Endo
9042
(p-C
lC6H
4CH
2)2Sn(L1)C
l1
483ndash673
5470
1054
5523
1067
Exo
minus2169
2723ndash793
25529
3942
23849
3764
Exo
minus9246
3873ndash973
38294
4745
38048
4785
Endo
9291
(C6H
5CH
2)3Sn(L2)C
l1
473ndash653
3829
697
4046
795
Exo
minus3046
2723ndash813
8703
1206
9534
1383
Exo
minus5249
3893ndash1003
20812
2410
21731
2622
Endo
11112
(p-C
lC6H
4CH
2)3Sn(L2)C
l1
423ndash623
3191
620
3491
741
Exo
minus2962
2703ndash753
25529
4162
25021
4069
Exo
minus5162
3873ndash973
2393
33041
25095
3189
Endo
11342
(C6H
5CH
2)2Sn(L2)C
l 21
493ndash653
5744
1120
5855
1135
Exo
minus2994
2703ndash773
2815
74369
27433
4344
Exo
minus5160
3873ndash993
17632
2142
17857
2157
Endo
11021
(p-C
lC6H
4CH
2)2Sn(L2)C
l 21
473ndash653
5444
784
5645
826
Exo
minus3106
2723ndash793
1914
72947
19218
2971
Exo
minus5206
3873ndash973
23753
2901
24328
2999
Endo
11226
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
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ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 3
and theobromine (L2) were synthesized according to theprocedure reported by Bhatia et al [32]
A solution of theophylline (HL1 180 g 001mol) in 25mLTHF and 5 gNaOH was stirred for about 12 hrs at room tem-perature A solution of R
3SnCl or R
2SnCl2(001mol) in 25mL
THF was added to it and stirred for 4H at room temperatureThe contents were then filtered and the filtratewas reduced toone-fourth of its original volume The R
3SnL1 or R
2Sn(L1)Cl
complexes precipitated out on adding petroleum ether andwere recrystallised from acetone Theobromine complexeswere synthesized by simply adding a solution of R
3SnCl
or R2SnCl2(001mol) in 25mL THF to a suspension of
theobromine (L2 180 g 001mol) in 25mL THF and stirredfor 3 hours at room temperature The contents were filteredand volume was reduced to one-fourth of its original volumeThe R
3SnL2(Cl) or R
2Sn(L2)Cl
2complexes precipitated out
on addition of petroleum ether and were recrystallised fromacetone
3 Results and Discussion
Elemental analyses reveal that the complexes are of goodpurity and are yellow in colourThe complexes were found tobe soluble in acetonitrile THF DMSO acetone and CHCl
3
The complexes decomposed before melting The analyticaldata of the complexes along with their decomposition tem-perature is given in Table 1 From the analytical data it is clearthat organotin(IV) derivatives react with these ligands in1 1 molar proportions Conductancemeasurements for thesecomplexes in 10minus2M nitrobenzene solution are in the rangeof 012ndash040 ohmminus1 cm2molminus1 indicating that the complexesare nonelectrolytes
31 Infrared Studies In case of theophylline complexes theligand can chelate with the metal ion either through C(6)carbonyl and N(7) or through N(7) alone [24 32 33] In thepresent case the ](C=O) stretching frequency for free ligandwas observed at 1720 and 1660 cmminus1 On complexation thepeaks merged and appeared at ca 1700 cmminus1 However thisshift cannot be attributed to the interaction of carbonyl atC(6) with Sn(IV) since the electronic spectra of these com-plexes rules out this possibility Further the disappearanceof the band at 3200 cmminus1 due to ](NndashH) stretching in thecomplexes indicate that the ligand is linked to Sn(IV) throughthe deprotonation of N(7)
In case of free theobromine the ](C=O) stretching fre-quency appears at 1700 and 1665 cmminus1 and remains unalteredon complexation However the ](C=N) + ](C=C) stretchingfrequency is shifted from 1595 and 1550 cmminus1 in free theo-bromine to ca 1580 and 1530 cmminus1 in complexes indicatingthat the theobromine is linked to Sn(IV) through N(9) [34]
32 Electronic Spectra In the electronic spectra of theo-phylline and theobromine the band corresponding to 120587 rarr120587lowast transition of the carbonyl group at 270 nm (log120576 345) and
272 nm (log120576 35) respectively almost remained unperturbed
on complexation confirming the noninvolvement of the car-bonyl group of these ligands in complexation [32] Additionalpeaks at sim210 nm and sim250 nm corresponding to the phenylring of R moiety are observed in case of the UV spectrumof metal complexes In addition to this the ligand rarr metalcharge transfer band is observed in the region 320ndash340 nm(log 120576 sim 42) in the complexes
33 1H and 13C NMR Studies The 1H NMR data of thecomplexes are tabulated in Tables 2 and 3 The peaksundergo a slight downfield shift on complexation due tothe change in the electronic environment of the ligand Intheophylline the broad peak due to ndashNndashH (120575 104) disappearson complexation confirming that the complexation involvesthe replacement of hydrogen atom in ndashNndashHndash group In theo-bromine the peak corresponding to H-8 (120575 71) undergoessignificant downfield shift on complexation confirming theinvolvement ofN-9 in complexation [35] 13CNMRdata havebeen recorded for both the ligands and their correspondingorganotin(IV) complexes and these spectra also support theauthenticity of the proposed structures (C
6H5CH2)3Sn(L1)
13CNMR ppm theophyllinato C(2) 1558 C(3) 1495 C(5)1073 C(6) 1623 C(8) 1411 1-Me 284 3-Me 301 SnndashCH2 1787 aromatic 1418 1306 1288 1317 1279 1316
(C6H5CH2)3Sn(L2)Cl theobromine C(2) 1511 C(4) 1495
C(5) 1063 C(6) 1612 C(8) 1365 3-Me 291 7-Me 284 SnndashCH2 1956 aromatic 1428 1316 1298 1327 1289 1326
34 Mass Studies The fragmentation pattern of the com-plexes has been analysed on the basis of mass spectra TheRSn+ R+ and Sn+ ions dominate the mass spectra Thecarbonium ion R+ constitutes the base peak in the massspectra of all the complexes Schemes 1 and 2 representthe fragmentation pattern for theophylline and theobrominemoieties respectively in the organotin(IV) complexes
35 Thermal Studies Thermal studies have been carriedout for all the complexes The thermogravimetric (TG)studies reveal that only two of the prepared complexes(C6H5CH2)3Sn(L1) and (p-ClC
6H4CH2)3Sn(L1) undergo
decomposition in two steps whereas the rest undergo decom-position in three stepsThe first step (423ndash673K) involves theloss of R groups the second step corresponds to the loss ofchlorine atom(s) and the final step involves the formationof SnO
2 The mass loss data is given in Table 4 The DTA
curves reveal that all the decomposition steps except the stepcorresponding to the formation of SnO
2 are exothermic in
nature The last step corresponding to the formation of SnO2
is endothermic in natureThe order (119899) and activation energy (119864
119886) have been
elucidated for the various steps using Coats-Redfern [36]as well as Horowitz-Metzger [37] methods The values ofactivation energy and entropy of the reaction have beencalculated using both methods and found to be in closeagreement The order of reaction in each case is one ΔH(enthalpy of reaction) have been calculated using the TG [38]andDTA curves respectively [39 40]The kinetic parameters
4 Journal of Chemistry
Table1Ph
ysicalcharacteris
ticsa
ndanalyticaldataof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Empiric
alform
ula
MolW
tfoun
d(cal)
Decptemp(∘C)Λ119887(Cminus15
9times10minus2M)
Foun
d(cal)
SnCl
NC
H(C
6H5C
H2)
3Sn(L1)
C 28H
28N
4SnO
257076
(57124)
210
021
2019
(2077)
mdash96
1(98
0)5864(5887)
461
(494)
(p-C
lC6H
4CH
2)3Sn(L1)
C 28H
25N
4SnO
2Cl 3
67321
(67398)
170
019
1705
(176
1)1522(1569)
798(831
)4962(498
9)321
(373)
(C6H
5CH
2)2Sn(L1)C
lC 2
1H21N
4SnO
2Cl
51491
(51536)
240
024
2262(2303)
629
(684)
1038(1087)
4869(4894)
392
(410
)(p-C
lC6H
4CH
2)2Sn(L1)C
lC 2
1H21N
4SnO
2Cl
58261
(58385)
210
039
2006(2032)
1768
(1811)
926(959)
4299(4320)
302
(328)
(C6H
5CH
2)3Sn(L2)C
lC 2
8H29N
4SnO
2Cl
60681
(60750)
200
021
1916
(1953
)534
(580)
906(922)
5501(5535
)451
(481)
(p-C
lC6H
4CH
2)3Sn(L2)C
lC 2
8H26N
4SnO
2Cl 4
7092
9(71024)
150
029
1621(1671)
1931
(1985)
762(788)
4711
(4735)
329
(369)
(C6H
5CH
2)2Sn(L2)C
l 2C 2
1H22N
4SnO
2Cl 2
5510
0(55162)
220
030
2112
(215
1)1221(1278)
998(1015)
4554(4572)
365
(402)
(p-C
lC6H
4CH
2)2Sn(L2)C
l 2C 2
1H20N
4SnO
2Cl 4
6197
9(62011)
200
032
1869(19
14)
2219
(2273)
889
(903)
4021(40
67)
302
(325)
Journal of Chemistry 5
Table2
1 Hand
13CNMRdata(120575
ppm)o
ftheop
hylline
complexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theoph
yllin
emoiety
ArndashH
ndashCH
2ndashH-8
ndashCH
3atN-3
ndashCH
3atN-1
ndashNHndash
Theoph
yllin
e(HL1)
mdashmdash
75-76(d1H
)36-37(s3H)
32(s3H)
104ndash106(br2
H)
(C6H
5CH
2)3Sn(L1)
79ndash81(m
15H
)36-37(s6H)
77-78(d1H
)39-40(s3H)
33(s3H)
mdash1787
(p-C
lC6H
4CH
2)3Sn(L1)
80ndash
82(m
12H
)39(s6H)
76-77(d1H
)41-4
2(s3H)
34(s3H)
mdash2401
(C6H
5CH
2)2Sn(L1)C
l79
-80(m
10H
)38(s4H)
75-76(d1H
)40-41(s3
H)
33-34(s3H)
mdash1721
(p-C
lC6H
4CH
2)2Sn(L1)C
l80-81(m8H)
37-38(s4H)
77-78(d1H
)40(s3H)
34-35(s3H)
mdash2350
6 Journal of Chemistry
Table3
1 Hand
13CNMRdata(120575
ppm)o
ftheob
rominec
omplexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theobrom
inem
oiety
ArndashH
ndashCH
2ndashndashC
H3atN-3
ndashCH
3atN-2
H-8
ndashNHndash
Theobrom
ine(L2)
mdashmdash
33(s3H)
35(s3H)
71(s1H)
130ndash132(br1H
)(C
6H5C
H2)
3Sn(L2)C
l70
ndash74(m
15H
)38-39(s6H)
34-35(s3H)
36-37(s3H)
77(s1H)
132ndash134(br1H
)1956
(p-C
lC6H
4CH
2)3Sn(L2)C
l71ndash73(m
12H
)39(s6H)
33-34(s3H)
36-37(s3H)
76(s1H)
134ndash136(br1H
)2534
(C6H
5CH
2)2Sn(L2)C
l 270
ndash73(m
10H
)39-40(s4H)
34(s3H)
37(s3H)
75(s1H)
133ndash135(br1H
)1834
(p-C
lC6H
4CH
2)2Sn(L2)C
l 271ndash73(m
8H)
38(s4H)
33-34(s3H)
36(s3H)
78(s1H)
133ndash136(br1H
)2366
Journal of Chemistry 7
+
+
+
N
N
O
O
N
N
N
N
O
O
N
N+
Sn
Sn
Sn
N
N
O
O
N
N
R
R
RR
R
R
R
R
R
CH3
CH3 CH3
CH3
CH3
CH3
∙
∙
∙∙
∙
∙+
C7H7N4O2
+
me 17906
C7H7N4O2
+
me 17906
C6H5N3O2
+
me 15104
C7H7N4O2
∙
me 17906
minusHCN
minusHNC
NH
N
N
O
O
N
NH C
HN
C
O
O
NH
NH
N
N
N
N
NH
CH
CH CH
CH
N
N
H
(b)
(a)
O
CH3
CH3
CH3
CH3
+
+
+
+
C
N
N
minusCO
minusCO
+ C
C4H5N3
me 9505
C5H5N3O∙+
me 12304
N
N
O
O
N
N
N
N
O
O
N
N
+
+
+
+N
N
O
O
N
N
R
R
R
Sn
Sn
Sn R
R
R
R
R
R
CH3
CH3
CH3
CH3
CH3
CH3∙
∙
∙+
C7H7N4O2
+
me 17905
C7H7N4O2
∙
me 17905
Scheme 1 Fragmentation pattern for theophylline complexes
8 Journal of Chemistry
+
+
N
N
O
O
N
N
H
N
N
O
O
N
N
H
Cl
N
N
O
O
N
N
H
R R
R
Sn
Sn
R R
Cl R
CH3
CH3
CH3
CH3CH3
CH3
∙+
∙+
∙+
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 180
C5H8N3
me 109
C5H7N3
me 109
C4H5N2
me 82
C4H5Nme 67
N
N
O
O
N
N
H
NO
N
N
H
minusHCNminusHCN
minusHNCON
N
O
N
N
NCH
NCH
CHCHN
N
N
N
H
(b)
(a)
Nme 55
NHC
NH
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3CH3 ∙+
∙
∙
∙
∙+
∙+
N
N
N
minusCO
C6H7N3O∙+
me 137
O+
C+
+N
N
O
O
N
N
H
Sn
N
N
O
O
N
N
H
N
N
O
O
N
N
H
R R
RCl
Cl
Cl
R R
R
Sn
Sn
R R
R+
CH3
CH3
CH3
CH3
CH3
CH3∙+
∙+
∙+
C7H8N4O2
∙+
me 180
C7H8N4O2
me 180
Scheme 2 Fragmentation pattern for theobromine complexes
Journal of Chemistry 9
Table 4 Phenomenological data for the thermal decomposition of the complexes
Complex Step number TG plateaux (K) Mass loss Nature of lossObserved Calc
(C6H5CH2)3Sn(L1) I 483ndash673 460 4786 Loss of 3 benzyl groups
II 893ndash1003 720 7373 Formation of SnO2
(p-ClC6H4CH2)3Sn(L1) I 443ndash633 550 5580 Loss of 3 p-chlorobenzyl groups
II 873ndash973 750 7773 Formation of SnO2
(C6H5CH2)2Sn(L1)Cl
I 513ndash663 347 3536 Loss of 2 benzyl groupsII 703ndash773 420 4220 Loss of chlorine atomIII 893ndash973 694 7088 Formation of SnO2
(p-ClC6H4CH2)2Sn(L1)Cl
I 483ndash673 420 4294 Loss of 2 p-chlorobenzyl groupsII 723ndash793 470 4898 Loss of chlorine atomIII 873ndash973 735 7429 Formation of SnO2
(C6H5CH2)3Sn(L2)Cl
I 473ndash653 450 450 Loss of 3 benzyl groupsII 723ndash813 500 5080 Loss of chlorine atomIII 893ndash1003 740 7529 Formation of SnO2
(p-ClC6H4CH2)3Sn(L2)Cl
I 423ndash623 520 5295 Loss of 3 p-chlorobenzyl groupsII 703ndash753 570 5792 Loss of chlorine atomIII 873ndash973 780 7887 Formation of SnO2
(C6H5CH2)2Sn(L2)Cl2
I 493ndash653 320 3304 Loss of 2 benzyl groupsII 703ndash773 450 4582 Loss of chlorine atomsIII 873ndash993 710 7279 Formation of SnO2
(p-ClC6H4CH2)2Sn(L2)Cl2
I 473ndash653 400 4043 Loss of 2 p-chlorobenzyl groupsII 723ndash793 500 5180 Loss of chlorine atomsIII 873ndash973 750 7580 Formation of SnO2
for the thermal decomposition of the complexes are given inTable 5
On the basis of the above data it can be concludedthat the complexes with R = p-ClC
6H4CH2ndash have lower 119864
119886
value for step 1 as compared to the complexes with the samenumber of R groups but R = C
6H5CH2ndash because the electron
withdrawing effect of chlorine makes the RndashSn bond weakerand facilitates its thermal degradation Moreover tri(p-chlorobenzyl)tin derivative has the least activation energy forthe first step due to the greater steric hindrance
36 In Vitro Antibacterial Studies Themetal complexes werescreened versus Ecoli S aureus and P pyocyanea bacterialstrains using the respective ligands as the standard forcomparing the activities The samples were screened at threedifferent concentrations (25 50 and 100 120583g cmminus3) in DMFThe inhibitory power of the metal complexes was observedto be greater than that of the control The general orderof activity versus the three microorganisms is Saureus gt Ppyocyanea gt EcoliThe data is presented in Table 6
37 Antifungal Studies The results reported in Table 7 revealthat the organotin complexes with these ligands are muchmore active than the parent ligand against the same microor-ganisms With increase in concentration of the compoundsthere occurs increase in percentage of inhibition Higherconcentration proves inhibitory for fungal growth
Sn
Cl
ClCl
Cl
N
N
N
N
OH
OCH3
CH2
CH2
H3C
Figure 2
On the basis of spectral evidence Figure 2 representingcoordination has been prepared for one of the complexessynthesized
Conflict of Interests
The authors declare that they have no conflict of interests
10 Journal of Chemistry
Table5Kinetic
parametersfor
thetherm
aldecompo
sitionof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Step
number
TempK
Coats-
Redfernmetho
dHorow
itz-M
etzger
metho
dDTA
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
Thermaleffect
Δ119867
(Jgminus
1 )
(C6H
5CH
2)3Sn(L1)
1483ndash673
5109
941
5423
1046
Exo
minus2042
2893ndash1003
30635
3762
31017
3801
Endo
9446
(p-C
lC6H
4CH
2)3Sn(L1)
144
3ndash633
4030
850
4184
881
Exo
minus1746
2873ndash973
21882
2742
24323
2982
Endo
9326
(C6H
5CH
2)2Sn(L1)C
l1
513ndash663
6382
1200
6562
1233
Exo
minus2210
2703ndash773
1915
43206
2114
03326
Exo
minus8999
3893ndash973
36698
4541
35353
443
Endo
9042
(p-C
lC6H
4CH
2)2Sn(L1)C
l1
483ndash673
5470
1054
5523
1067
Exo
minus2169
2723ndash793
25529
3942
23849
3764
Exo
minus9246
3873ndash973
38294
4745
38048
4785
Endo
9291
(C6H
5CH
2)3Sn(L2)C
l1
473ndash653
3829
697
4046
795
Exo
minus3046
2723ndash813
8703
1206
9534
1383
Exo
minus5249
3893ndash1003
20812
2410
21731
2622
Endo
11112
(p-C
lC6H
4CH
2)3Sn(L2)C
l1
423ndash623
3191
620
3491
741
Exo
minus2962
2703ndash753
25529
4162
25021
4069
Exo
minus5162
3873ndash973
2393
33041
25095
3189
Endo
11342
(C6H
5CH
2)2Sn(L2)C
l 21
493ndash653
5744
1120
5855
1135
Exo
minus2994
2703ndash773
2815
74369
27433
4344
Exo
minus5160
3873ndash993
17632
2142
17857
2157
Endo
11021
(p-C
lC6H
4CH
2)2Sn(L2)C
l 21
473ndash653
5444
784
5645
826
Exo
minus3106
2723ndash793
1914
72947
19218
2971
Exo
minus5206
3873ndash973
23753
2901
24328
2999
Endo
11226
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Carbohydrate Chemistry
International Journal of
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Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Medicinal ChemistryInternational Journal of
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Analytical ChemistryInternational Journal of
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ElectrochemistryInternational Journal of
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CatalystsJournal of
4 Journal of Chemistry
Table1Ph
ysicalcharacteris
ticsa
ndanalyticaldataof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Empiric
alform
ula
MolW
tfoun
d(cal)
Decptemp(∘C)Λ119887(Cminus15
9times10minus2M)
Foun
d(cal)
SnCl
NC
H(C
6H5C
H2)
3Sn(L1)
C 28H
28N
4SnO
257076
(57124)
210
021
2019
(2077)
mdash96
1(98
0)5864(5887)
461
(494)
(p-C
lC6H
4CH
2)3Sn(L1)
C 28H
25N
4SnO
2Cl 3
67321
(67398)
170
019
1705
(176
1)1522(1569)
798(831
)4962(498
9)321
(373)
(C6H
5CH
2)2Sn(L1)C
lC 2
1H21N
4SnO
2Cl
51491
(51536)
240
024
2262(2303)
629
(684)
1038(1087)
4869(4894)
392
(410
)(p-C
lC6H
4CH
2)2Sn(L1)C
lC 2
1H21N
4SnO
2Cl
58261
(58385)
210
039
2006(2032)
1768
(1811)
926(959)
4299(4320)
302
(328)
(C6H
5CH
2)3Sn(L2)C
lC 2
8H29N
4SnO
2Cl
60681
(60750)
200
021
1916
(1953
)534
(580)
906(922)
5501(5535
)451
(481)
(p-C
lC6H
4CH
2)3Sn(L2)C
lC 2
8H26N
4SnO
2Cl 4
7092
9(71024)
150
029
1621(1671)
1931
(1985)
762(788)
4711
(4735)
329
(369)
(C6H
5CH
2)2Sn(L2)C
l 2C 2
1H22N
4SnO
2Cl 2
5510
0(55162)
220
030
2112
(215
1)1221(1278)
998(1015)
4554(4572)
365
(402)
(p-C
lC6H
4CH
2)2Sn(L2)C
l 2C 2
1H20N
4SnO
2Cl 4
6197
9(62011)
200
032
1869(19
14)
2219
(2273)
889
(903)
4021(40
67)
302
(325)
Journal of Chemistry 5
Table2
1 Hand
13CNMRdata(120575
ppm)o
ftheop
hylline
complexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theoph
yllin
emoiety
ArndashH
ndashCH
2ndashH-8
ndashCH
3atN-3
ndashCH
3atN-1
ndashNHndash
Theoph
yllin
e(HL1)
mdashmdash
75-76(d1H
)36-37(s3H)
32(s3H)
104ndash106(br2
H)
(C6H
5CH
2)3Sn(L1)
79ndash81(m
15H
)36-37(s6H)
77-78(d1H
)39-40(s3H)
33(s3H)
mdash1787
(p-C
lC6H
4CH
2)3Sn(L1)
80ndash
82(m
12H
)39(s6H)
76-77(d1H
)41-4
2(s3H)
34(s3H)
mdash2401
(C6H
5CH
2)2Sn(L1)C
l79
-80(m
10H
)38(s4H)
75-76(d1H
)40-41(s3
H)
33-34(s3H)
mdash1721
(p-C
lC6H
4CH
2)2Sn(L1)C
l80-81(m8H)
37-38(s4H)
77-78(d1H
)40(s3H)
34-35(s3H)
mdash2350
6 Journal of Chemistry
Table3
1 Hand
13CNMRdata(120575
ppm)o
ftheob
rominec
omplexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theobrom
inem
oiety
ArndashH
ndashCH
2ndashndashC
H3atN-3
ndashCH
3atN-2
H-8
ndashNHndash
Theobrom
ine(L2)
mdashmdash
33(s3H)
35(s3H)
71(s1H)
130ndash132(br1H
)(C
6H5C
H2)
3Sn(L2)C
l70
ndash74(m
15H
)38-39(s6H)
34-35(s3H)
36-37(s3H)
77(s1H)
132ndash134(br1H
)1956
(p-C
lC6H
4CH
2)3Sn(L2)C
l71ndash73(m
12H
)39(s6H)
33-34(s3H)
36-37(s3H)
76(s1H)
134ndash136(br1H
)2534
(C6H
5CH
2)2Sn(L2)C
l 270
ndash73(m
10H
)39-40(s4H)
34(s3H)
37(s3H)
75(s1H)
133ndash135(br1H
)1834
(p-C
lC6H
4CH
2)2Sn(L2)C
l 271ndash73(m
8H)
38(s4H)
33-34(s3H)
36(s3H)
78(s1H)
133ndash136(br1H
)2366
Journal of Chemistry 7
+
+
+
N
N
O
O
N
N
N
N
O
O
N
N+
Sn
Sn
Sn
N
N
O
O
N
N
R
R
RR
R
R
R
R
R
CH3
CH3 CH3
CH3
CH3
CH3
∙
∙
∙∙
∙
∙+
C7H7N4O2
+
me 17906
C7H7N4O2
+
me 17906
C6H5N3O2
+
me 15104
C7H7N4O2
∙
me 17906
minusHCN
minusHNC
NH
N
N
O
O
N
NH C
HN
C
O
O
NH
NH
N
N
N
N
NH
CH
CH CH
CH
N
N
H
(b)
(a)
O
CH3
CH3
CH3
CH3
+
+
+
+
C
N
N
minusCO
minusCO
+ C
C4H5N3
me 9505
C5H5N3O∙+
me 12304
N
N
O
O
N
N
N
N
O
O
N
N
+
+
+
+N
N
O
O
N
N
R
R
R
Sn
Sn
Sn R
R
R
R
R
R
CH3
CH3
CH3
CH3
CH3
CH3∙
∙
∙+
C7H7N4O2
+
me 17905
C7H7N4O2
∙
me 17905
Scheme 1 Fragmentation pattern for theophylline complexes
8 Journal of Chemistry
+
+
N
N
O
O
N
N
H
N
N
O
O
N
N
H
Cl
N
N
O
O
N
N
H
R R
R
Sn
Sn
R R
Cl R
CH3
CH3
CH3
CH3CH3
CH3
∙+
∙+
∙+
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 180
C5H8N3
me 109
C5H7N3
me 109
C4H5N2
me 82
C4H5Nme 67
N
N
O
O
N
N
H
NO
N
N
H
minusHCNminusHCN
minusHNCON
N
O
N
N
NCH
NCH
CHCHN
N
N
N
H
(b)
(a)
Nme 55
NHC
NH
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3CH3 ∙+
∙
∙
∙
∙+
∙+
N
N
N
minusCO
C6H7N3O∙+
me 137
O+
C+
+N
N
O
O
N
N
H
Sn
N
N
O
O
N
N
H
N
N
O
O
N
N
H
R R
RCl
Cl
Cl
R R
R
Sn
Sn
R R
R+
CH3
CH3
CH3
CH3
CH3
CH3∙+
∙+
∙+
C7H8N4O2
∙+
me 180
C7H8N4O2
me 180
Scheme 2 Fragmentation pattern for theobromine complexes
Journal of Chemistry 9
Table 4 Phenomenological data for the thermal decomposition of the complexes
Complex Step number TG plateaux (K) Mass loss Nature of lossObserved Calc
(C6H5CH2)3Sn(L1) I 483ndash673 460 4786 Loss of 3 benzyl groups
II 893ndash1003 720 7373 Formation of SnO2
(p-ClC6H4CH2)3Sn(L1) I 443ndash633 550 5580 Loss of 3 p-chlorobenzyl groups
II 873ndash973 750 7773 Formation of SnO2
(C6H5CH2)2Sn(L1)Cl
I 513ndash663 347 3536 Loss of 2 benzyl groupsII 703ndash773 420 4220 Loss of chlorine atomIII 893ndash973 694 7088 Formation of SnO2
(p-ClC6H4CH2)2Sn(L1)Cl
I 483ndash673 420 4294 Loss of 2 p-chlorobenzyl groupsII 723ndash793 470 4898 Loss of chlorine atomIII 873ndash973 735 7429 Formation of SnO2
(C6H5CH2)3Sn(L2)Cl
I 473ndash653 450 450 Loss of 3 benzyl groupsII 723ndash813 500 5080 Loss of chlorine atomIII 893ndash1003 740 7529 Formation of SnO2
(p-ClC6H4CH2)3Sn(L2)Cl
I 423ndash623 520 5295 Loss of 3 p-chlorobenzyl groupsII 703ndash753 570 5792 Loss of chlorine atomIII 873ndash973 780 7887 Formation of SnO2
(C6H5CH2)2Sn(L2)Cl2
I 493ndash653 320 3304 Loss of 2 benzyl groupsII 703ndash773 450 4582 Loss of chlorine atomsIII 873ndash993 710 7279 Formation of SnO2
(p-ClC6H4CH2)2Sn(L2)Cl2
I 473ndash653 400 4043 Loss of 2 p-chlorobenzyl groupsII 723ndash793 500 5180 Loss of chlorine atomsIII 873ndash973 750 7580 Formation of SnO2
for the thermal decomposition of the complexes are given inTable 5
On the basis of the above data it can be concludedthat the complexes with R = p-ClC
6H4CH2ndash have lower 119864
119886
value for step 1 as compared to the complexes with the samenumber of R groups but R = C
6H5CH2ndash because the electron
withdrawing effect of chlorine makes the RndashSn bond weakerand facilitates its thermal degradation Moreover tri(p-chlorobenzyl)tin derivative has the least activation energy forthe first step due to the greater steric hindrance
36 In Vitro Antibacterial Studies Themetal complexes werescreened versus Ecoli S aureus and P pyocyanea bacterialstrains using the respective ligands as the standard forcomparing the activities The samples were screened at threedifferent concentrations (25 50 and 100 120583g cmminus3) in DMFThe inhibitory power of the metal complexes was observedto be greater than that of the control The general orderof activity versus the three microorganisms is Saureus gt Ppyocyanea gt EcoliThe data is presented in Table 6
37 Antifungal Studies The results reported in Table 7 revealthat the organotin complexes with these ligands are muchmore active than the parent ligand against the same microor-ganisms With increase in concentration of the compoundsthere occurs increase in percentage of inhibition Higherconcentration proves inhibitory for fungal growth
Sn
Cl
ClCl
Cl
N
N
N
N
OH
OCH3
CH2
CH2
H3C
Figure 2
On the basis of spectral evidence Figure 2 representingcoordination has been prepared for one of the complexessynthesized
Conflict of Interests
The authors declare that they have no conflict of interests
10 Journal of Chemistry
Table5Kinetic
parametersfor
thetherm
aldecompo
sitionof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Step
number
TempK
Coats-
Redfernmetho
dHorow
itz-M
etzger
metho
dDTA
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
Thermaleffect
Δ119867
(Jgminus
1 )
(C6H
5CH
2)3Sn(L1)
1483ndash673
5109
941
5423
1046
Exo
minus2042
2893ndash1003
30635
3762
31017
3801
Endo
9446
(p-C
lC6H
4CH
2)3Sn(L1)
144
3ndash633
4030
850
4184
881
Exo
minus1746
2873ndash973
21882
2742
24323
2982
Endo
9326
(C6H
5CH
2)2Sn(L1)C
l1
513ndash663
6382
1200
6562
1233
Exo
minus2210
2703ndash773
1915
43206
2114
03326
Exo
minus8999
3893ndash973
36698
4541
35353
443
Endo
9042
(p-C
lC6H
4CH
2)2Sn(L1)C
l1
483ndash673
5470
1054
5523
1067
Exo
minus2169
2723ndash793
25529
3942
23849
3764
Exo
minus9246
3873ndash973
38294
4745
38048
4785
Endo
9291
(C6H
5CH
2)3Sn(L2)C
l1
473ndash653
3829
697
4046
795
Exo
minus3046
2723ndash813
8703
1206
9534
1383
Exo
minus5249
3893ndash1003
20812
2410
21731
2622
Endo
11112
(p-C
lC6H
4CH
2)3Sn(L2)C
l1
423ndash623
3191
620
3491
741
Exo
minus2962
2703ndash753
25529
4162
25021
4069
Exo
minus5162
3873ndash973
2393
33041
25095
3189
Endo
11342
(C6H
5CH
2)2Sn(L2)C
l 21
493ndash653
5744
1120
5855
1135
Exo
minus2994
2703ndash773
2815
74369
27433
4344
Exo
minus5160
3873ndash993
17632
2142
17857
2157
Endo
11021
(p-C
lC6H
4CH
2)2Sn(L2)C
l 21
473ndash653
5444
784
5645
826
Exo
minus3106
2723ndash793
1914
72947
19218
2971
Exo
minus5206
3873ndash973
23753
2901
24328
2999
Endo
11226
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 5
Table2
1 Hand
13CNMRdata(120575
ppm)o
ftheop
hylline
complexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theoph
yllin
emoiety
ArndashH
ndashCH
2ndashH-8
ndashCH
3atN-3
ndashCH
3atN-1
ndashNHndash
Theoph
yllin
e(HL1)
mdashmdash
75-76(d1H
)36-37(s3H)
32(s3H)
104ndash106(br2
H)
(C6H
5CH
2)3Sn(L1)
79ndash81(m
15H
)36-37(s6H)
77-78(d1H
)39-40(s3H)
33(s3H)
mdash1787
(p-C
lC6H
4CH
2)3Sn(L1)
80ndash
82(m
12H
)39(s6H)
76-77(d1H
)41-4
2(s3H)
34(s3H)
mdash2401
(C6H
5CH
2)2Sn(L1)C
l79
-80(m
10H
)38(s4H)
75-76(d1H
)40-41(s3
H)
33-34(s3H)
mdash1721
(p-C
lC6H
4CH
2)2Sn(L1)C
l80-81(m8H)
37-38(s4H)
77-78(d1H
)40(s3H)
34-35(s3H)
mdash2350
6 Journal of Chemistry
Table3
1 Hand
13CNMRdata(120575
ppm)o
ftheob
rominec
omplexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theobrom
inem
oiety
ArndashH
ndashCH
2ndashndashC
H3atN-3
ndashCH
3atN-2
H-8
ndashNHndash
Theobrom
ine(L2)
mdashmdash
33(s3H)
35(s3H)
71(s1H)
130ndash132(br1H
)(C
6H5C
H2)
3Sn(L2)C
l70
ndash74(m
15H
)38-39(s6H)
34-35(s3H)
36-37(s3H)
77(s1H)
132ndash134(br1H
)1956
(p-C
lC6H
4CH
2)3Sn(L2)C
l71ndash73(m
12H
)39(s6H)
33-34(s3H)
36-37(s3H)
76(s1H)
134ndash136(br1H
)2534
(C6H
5CH
2)2Sn(L2)C
l 270
ndash73(m
10H
)39-40(s4H)
34(s3H)
37(s3H)
75(s1H)
133ndash135(br1H
)1834
(p-C
lC6H
4CH
2)2Sn(L2)C
l 271ndash73(m
8H)
38(s4H)
33-34(s3H)
36(s3H)
78(s1H)
133ndash136(br1H
)2366
Journal of Chemistry 7
+
+
+
N
N
O
O
N
N
N
N
O
O
N
N+
Sn
Sn
Sn
N
N
O
O
N
N
R
R
RR
R
R
R
R
R
CH3
CH3 CH3
CH3
CH3
CH3
∙
∙
∙∙
∙
∙+
C7H7N4O2
+
me 17906
C7H7N4O2
+
me 17906
C6H5N3O2
+
me 15104
C7H7N4O2
∙
me 17906
minusHCN
minusHNC
NH
N
N
O
O
N
NH C
HN
C
O
O
NH
NH
N
N
N
N
NH
CH
CH CH
CH
N
N
H
(b)
(a)
O
CH3
CH3
CH3
CH3
+
+
+
+
C
N
N
minusCO
minusCO
+ C
C4H5N3
me 9505
C5H5N3O∙+
me 12304
N
N
O
O
N
N
N
N
O
O
N
N
+
+
+
+N
N
O
O
N
N
R
R
R
Sn
Sn
Sn R
R
R
R
R
R
CH3
CH3
CH3
CH3
CH3
CH3∙
∙
∙+
C7H7N4O2
+
me 17905
C7H7N4O2
∙
me 17905
Scheme 1 Fragmentation pattern for theophylline complexes
8 Journal of Chemistry
+
+
N
N
O
O
N
N
H
N
N
O
O
N
N
H
Cl
N
N
O
O
N
N
H
R R
R
Sn
Sn
R R
Cl R
CH3
CH3
CH3
CH3CH3
CH3
∙+
∙+
∙+
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 180
C5H8N3
me 109
C5H7N3
me 109
C4H5N2
me 82
C4H5Nme 67
N
N
O
O
N
N
H
NO
N
N
H
minusHCNminusHCN
minusHNCON
N
O
N
N
NCH
NCH
CHCHN
N
N
N
H
(b)
(a)
Nme 55
NHC
NH
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3CH3 ∙+
∙
∙
∙
∙+
∙+
N
N
N
minusCO
C6H7N3O∙+
me 137
O+
C+
+N
N
O
O
N
N
H
Sn
N
N
O
O
N
N
H
N
N
O
O
N
N
H
R R
RCl
Cl
Cl
R R
R
Sn
Sn
R R
R+
CH3
CH3
CH3
CH3
CH3
CH3∙+
∙+
∙+
C7H8N4O2
∙+
me 180
C7H8N4O2
me 180
Scheme 2 Fragmentation pattern for theobromine complexes
Journal of Chemistry 9
Table 4 Phenomenological data for the thermal decomposition of the complexes
Complex Step number TG plateaux (K) Mass loss Nature of lossObserved Calc
(C6H5CH2)3Sn(L1) I 483ndash673 460 4786 Loss of 3 benzyl groups
II 893ndash1003 720 7373 Formation of SnO2
(p-ClC6H4CH2)3Sn(L1) I 443ndash633 550 5580 Loss of 3 p-chlorobenzyl groups
II 873ndash973 750 7773 Formation of SnO2
(C6H5CH2)2Sn(L1)Cl
I 513ndash663 347 3536 Loss of 2 benzyl groupsII 703ndash773 420 4220 Loss of chlorine atomIII 893ndash973 694 7088 Formation of SnO2
(p-ClC6H4CH2)2Sn(L1)Cl
I 483ndash673 420 4294 Loss of 2 p-chlorobenzyl groupsII 723ndash793 470 4898 Loss of chlorine atomIII 873ndash973 735 7429 Formation of SnO2
(C6H5CH2)3Sn(L2)Cl
I 473ndash653 450 450 Loss of 3 benzyl groupsII 723ndash813 500 5080 Loss of chlorine atomIII 893ndash1003 740 7529 Formation of SnO2
(p-ClC6H4CH2)3Sn(L2)Cl
I 423ndash623 520 5295 Loss of 3 p-chlorobenzyl groupsII 703ndash753 570 5792 Loss of chlorine atomIII 873ndash973 780 7887 Formation of SnO2
(C6H5CH2)2Sn(L2)Cl2
I 493ndash653 320 3304 Loss of 2 benzyl groupsII 703ndash773 450 4582 Loss of chlorine atomsIII 873ndash993 710 7279 Formation of SnO2
(p-ClC6H4CH2)2Sn(L2)Cl2
I 473ndash653 400 4043 Loss of 2 p-chlorobenzyl groupsII 723ndash793 500 5180 Loss of chlorine atomsIII 873ndash973 750 7580 Formation of SnO2
for the thermal decomposition of the complexes are given inTable 5
On the basis of the above data it can be concludedthat the complexes with R = p-ClC
6H4CH2ndash have lower 119864
119886
value for step 1 as compared to the complexes with the samenumber of R groups but R = C
6H5CH2ndash because the electron
withdrawing effect of chlorine makes the RndashSn bond weakerand facilitates its thermal degradation Moreover tri(p-chlorobenzyl)tin derivative has the least activation energy forthe first step due to the greater steric hindrance
36 In Vitro Antibacterial Studies Themetal complexes werescreened versus Ecoli S aureus and P pyocyanea bacterialstrains using the respective ligands as the standard forcomparing the activities The samples were screened at threedifferent concentrations (25 50 and 100 120583g cmminus3) in DMFThe inhibitory power of the metal complexes was observedto be greater than that of the control The general orderof activity versus the three microorganisms is Saureus gt Ppyocyanea gt EcoliThe data is presented in Table 6
37 Antifungal Studies The results reported in Table 7 revealthat the organotin complexes with these ligands are muchmore active than the parent ligand against the same microor-ganisms With increase in concentration of the compoundsthere occurs increase in percentage of inhibition Higherconcentration proves inhibitory for fungal growth
Sn
Cl
ClCl
Cl
N
N
N
N
OH
OCH3
CH2
CH2
H3C
Figure 2
On the basis of spectral evidence Figure 2 representingcoordination has been prepared for one of the complexessynthesized
Conflict of Interests
The authors declare that they have no conflict of interests
10 Journal of Chemistry
Table5Kinetic
parametersfor
thetherm
aldecompo
sitionof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Step
number
TempK
Coats-
Redfernmetho
dHorow
itz-M
etzger
metho
dDTA
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
Thermaleffect
Δ119867
(Jgminus
1 )
(C6H
5CH
2)3Sn(L1)
1483ndash673
5109
941
5423
1046
Exo
minus2042
2893ndash1003
30635
3762
31017
3801
Endo
9446
(p-C
lC6H
4CH
2)3Sn(L1)
144
3ndash633
4030
850
4184
881
Exo
minus1746
2873ndash973
21882
2742
24323
2982
Endo
9326
(C6H
5CH
2)2Sn(L1)C
l1
513ndash663
6382
1200
6562
1233
Exo
minus2210
2703ndash773
1915
43206
2114
03326
Exo
minus8999
3893ndash973
36698
4541
35353
443
Endo
9042
(p-C
lC6H
4CH
2)2Sn(L1)C
l1
483ndash673
5470
1054
5523
1067
Exo
minus2169
2723ndash793
25529
3942
23849
3764
Exo
minus9246
3873ndash973
38294
4745
38048
4785
Endo
9291
(C6H
5CH
2)3Sn(L2)C
l1
473ndash653
3829
697
4046
795
Exo
minus3046
2723ndash813
8703
1206
9534
1383
Exo
minus5249
3893ndash1003
20812
2410
21731
2622
Endo
11112
(p-C
lC6H
4CH
2)3Sn(L2)C
l1
423ndash623
3191
620
3491
741
Exo
minus2962
2703ndash753
25529
4162
25021
4069
Exo
minus5162
3873ndash973
2393
33041
25095
3189
Endo
11342
(C6H
5CH
2)2Sn(L2)C
l 21
493ndash653
5744
1120
5855
1135
Exo
minus2994
2703ndash773
2815
74369
27433
4344
Exo
minus5160
3873ndash993
17632
2142
17857
2157
Endo
11021
(p-C
lC6H
4CH
2)2Sn(L2)C
l 21
473ndash653
5444
784
5645
826
Exo
minus3106
2723ndash793
1914
72947
19218
2971
Exo
minus5206
3873ndash973
23753
2901
24328
2999
Endo
11226
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
6 Journal of Chemistry
Table3
1 Hand
13CNMRdata(120575
ppm)o
ftheob
rominec
omplexes
Com
poun
d1 H
NMR
13CNMR
SnndashC
H2
ndashRmoiety
Theobrom
inem
oiety
ArndashH
ndashCH
2ndashndashC
H3atN-3
ndashCH
3atN-2
H-8
ndashNHndash
Theobrom
ine(L2)
mdashmdash
33(s3H)
35(s3H)
71(s1H)
130ndash132(br1H
)(C
6H5C
H2)
3Sn(L2)C
l70
ndash74(m
15H
)38-39(s6H)
34-35(s3H)
36-37(s3H)
77(s1H)
132ndash134(br1H
)1956
(p-C
lC6H
4CH
2)3Sn(L2)C
l71ndash73(m
12H
)39(s6H)
33-34(s3H)
36-37(s3H)
76(s1H)
134ndash136(br1H
)2534
(C6H
5CH
2)2Sn(L2)C
l 270
ndash73(m
10H
)39-40(s4H)
34(s3H)
37(s3H)
75(s1H)
133ndash135(br1H
)1834
(p-C
lC6H
4CH
2)2Sn(L2)C
l 271ndash73(m
8H)
38(s4H)
33-34(s3H)
36(s3H)
78(s1H)
133ndash136(br1H
)2366
Journal of Chemistry 7
+
+
+
N
N
O
O
N
N
N
N
O
O
N
N+
Sn
Sn
Sn
N
N
O
O
N
N
R
R
RR
R
R
R
R
R
CH3
CH3 CH3
CH3
CH3
CH3
∙
∙
∙∙
∙
∙+
C7H7N4O2
+
me 17906
C7H7N4O2
+
me 17906
C6H5N3O2
+
me 15104
C7H7N4O2
∙
me 17906
minusHCN
minusHNC
NH
N
N
O
O
N
NH C
HN
C
O
O
NH
NH
N
N
N
N
NH
CH
CH CH
CH
N
N
H
(b)
(a)
O
CH3
CH3
CH3
CH3
+
+
+
+
C
N
N
minusCO
minusCO
+ C
C4H5N3
me 9505
C5H5N3O∙+
me 12304
N
N
O
O
N
N
N
N
O
O
N
N
+
+
+
+N
N
O
O
N
N
R
R
R
Sn
Sn
Sn R
R
R
R
R
R
CH3
CH3
CH3
CH3
CH3
CH3∙
∙
∙+
C7H7N4O2
+
me 17905
C7H7N4O2
∙
me 17905
Scheme 1 Fragmentation pattern for theophylline complexes
8 Journal of Chemistry
+
+
N
N
O
O
N
N
H
N
N
O
O
N
N
H
Cl
N
N
O
O
N
N
H
R R
R
Sn
Sn
R R
Cl R
CH3
CH3
CH3
CH3CH3
CH3
∙+
∙+
∙+
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 180
C5H8N3
me 109
C5H7N3
me 109
C4H5N2
me 82
C4H5Nme 67
N
N
O
O
N
N
H
NO
N
N
H
minusHCNminusHCN
minusHNCON
N
O
N
N
NCH
NCH
CHCHN
N
N
N
H
(b)
(a)
Nme 55
NHC
NH
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3CH3 ∙+
∙
∙
∙
∙+
∙+
N
N
N
minusCO
C6H7N3O∙+
me 137
O+
C+
+N
N
O
O
N
N
H
Sn
N
N
O
O
N
N
H
N
N
O
O
N
N
H
R R
RCl
Cl
Cl
R R
R
Sn
Sn
R R
R+
CH3
CH3
CH3
CH3
CH3
CH3∙+
∙+
∙+
C7H8N4O2
∙+
me 180
C7H8N4O2
me 180
Scheme 2 Fragmentation pattern for theobromine complexes
Journal of Chemistry 9
Table 4 Phenomenological data for the thermal decomposition of the complexes
Complex Step number TG plateaux (K) Mass loss Nature of lossObserved Calc
(C6H5CH2)3Sn(L1) I 483ndash673 460 4786 Loss of 3 benzyl groups
II 893ndash1003 720 7373 Formation of SnO2
(p-ClC6H4CH2)3Sn(L1) I 443ndash633 550 5580 Loss of 3 p-chlorobenzyl groups
II 873ndash973 750 7773 Formation of SnO2
(C6H5CH2)2Sn(L1)Cl
I 513ndash663 347 3536 Loss of 2 benzyl groupsII 703ndash773 420 4220 Loss of chlorine atomIII 893ndash973 694 7088 Formation of SnO2
(p-ClC6H4CH2)2Sn(L1)Cl
I 483ndash673 420 4294 Loss of 2 p-chlorobenzyl groupsII 723ndash793 470 4898 Loss of chlorine atomIII 873ndash973 735 7429 Formation of SnO2
(C6H5CH2)3Sn(L2)Cl
I 473ndash653 450 450 Loss of 3 benzyl groupsII 723ndash813 500 5080 Loss of chlorine atomIII 893ndash1003 740 7529 Formation of SnO2
(p-ClC6H4CH2)3Sn(L2)Cl
I 423ndash623 520 5295 Loss of 3 p-chlorobenzyl groupsII 703ndash753 570 5792 Loss of chlorine atomIII 873ndash973 780 7887 Formation of SnO2
(C6H5CH2)2Sn(L2)Cl2
I 493ndash653 320 3304 Loss of 2 benzyl groupsII 703ndash773 450 4582 Loss of chlorine atomsIII 873ndash993 710 7279 Formation of SnO2
(p-ClC6H4CH2)2Sn(L2)Cl2
I 473ndash653 400 4043 Loss of 2 p-chlorobenzyl groupsII 723ndash793 500 5180 Loss of chlorine atomsIII 873ndash973 750 7580 Formation of SnO2
for the thermal decomposition of the complexes are given inTable 5
On the basis of the above data it can be concludedthat the complexes with R = p-ClC
6H4CH2ndash have lower 119864
119886
value for step 1 as compared to the complexes with the samenumber of R groups but R = C
6H5CH2ndash because the electron
withdrawing effect of chlorine makes the RndashSn bond weakerand facilitates its thermal degradation Moreover tri(p-chlorobenzyl)tin derivative has the least activation energy forthe first step due to the greater steric hindrance
36 In Vitro Antibacterial Studies Themetal complexes werescreened versus Ecoli S aureus and P pyocyanea bacterialstrains using the respective ligands as the standard forcomparing the activities The samples were screened at threedifferent concentrations (25 50 and 100 120583g cmminus3) in DMFThe inhibitory power of the metal complexes was observedto be greater than that of the control The general orderof activity versus the three microorganisms is Saureus gt Ppyocyanea gt EcoliThe data is presented in Table 6
37 Antifungal Studies The results reported in Table 7 revealthat the organotin complexes with these ligands are muchmore active than the parent ligand against the same microor-ganisms With increase in concentration of the compoundsthere occurs increase in percentage of inhibition Higherconcentration proves inhibitory for fungal growth
Sn
Cl
ClCl
Cl
N
N
N
N
OH
OCH3
CH2
CH2
H3C
Figure 2
On the basis of spectral evidence Figure 2 representingcoordination has been prepared for one of the complexessynthesized
Conflict of Interests
The authors declare that they have no conflict of interests
10 Journal of Chemistry
Table5Kinetic
parametersfor
thetherm
aldecompo
sitionof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Step
number
TempK
Coats-
Redfernmetho
dHorow
itz-M
etzger
metho
dDTA
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
Thermaleffect
Δ119867
(Jgminus
1 )
(C6H
5CH
2)3Sn(L1)
1483ndash673
5109
941
5423
1046
Exo
minus2042
2893ndash1003
30635
3762
31017
3801
Endo
9446
(p-C
lC6H
4CH
2)3Sn(L1)
144
3ndash633
4030
850
4184
881
Exo
minus1746
2873ndash973
21882
2742
24323
2982
Endo
9326
(C6H
5CH
2)2Sn(L1)C
l1
513ndash663
6382
1200
6562
1233
Exo
minus2210
2703ndash773
1915
43206
2114
03326
Exo
minus8999
3893ndash973
36698
4541
35353
443
Endo
9042
(p-C
lC6H
4CH
2)2Sn(L1)C
l1
483ndash673
5470
1054
5523
1067
Exo
minus2169
2723ndash793
25529
3942
23849
3764
Exo
minus9246
3873ndash973
38294
4745
38048
4785
Endo
9291
(C6H
5CH
2)3Sn(L2)C
l1
473ndash653
3829
697
4046
795
Exo
minus3046
2723ndash813
8703
1206
9534
1383
Exo
minus5249
3893ndash1003
20812
2410
21731
2622
Endo
11112
(p-C
lC6H
4CH
2)3Sn(L2)C
l1
423ndash623
3191
620
3491
741
Exo
minus2962
2703ndash753
25529
4162
25021
4069
Exo
minus5162
3873ndash973
2393
33041
25095
3189
Endo
11342
(C6H
5CH
2)2Sn(L2)C
l 21
493ndash653
5744
1120
5855
1135
Exo
minus2994
2703ndash773
2815
74369
27433
4344
Exo
minus5160
3873ndash993
17632
2142
17857
2157
Endo
11021
(p-C
lC6H
4CH
2)2Sn(L2)C
l 21
473ndash653
5444
784
5645
826
Exo
minus3106
2723ndash793
1914
72947
19218
2971
Exo
minus5206
3873ndash973
23753
2901
24328
2999
Endo
11226
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 7
+
+
+
N
N
O
O
N
N
N
N
O
O
N
N+
Sn
Sn
Sn
N
N
O
O
N
N
R
R
RR
R
R
R
R
R
CH3
CH3 CH3
CH3
CH3
CH3
∙
∙
∙∙
∙
∙+
C7H7N4O2
+
me 17906
C7H7N4O2
+
me 17906
C6H5N3O2
+
me 15104
C7H7N4O2
∙
me 17906
minusHCN
minusHNC
NH
N
N
O
O
N
NH C
HN
C
O
O
NH
NH
N
N
N
N
NH
CH
CH CH
CH
N
N
H
(b)
(a)
O
CH3
CH3
CH3
CH3
+
+
+
+
C
N
N
minusCO
minusCO
+ C
C4H5N3
me 9505
C5H5N3O∙+
me 12304
N
N
O
O
N
N
N
N
O
O
N
N
+
+
+
+N
N
O
O
N
N
R
R
R
Sn
Sn
Sn R
R
R
R
R
R
CH3
CH3
CH3
CH3
CH3
CH3∙
∙
∙+
C7H7N4O2
+
me 17905
C7H7N4O2
∙
me 17905
Scheme 1 Fragmentation pattern for theophylline complexes
8 Journal of Chemistry
+
+
N
N
O
O
N
N
H
N
N
O
O
N
N
H
Cl
N
N
O
O
N
N
H
R R
R
Sn
Sn
R R
Cl R
CH3
CH3
CH3
CH3CH3
CH3
∙+
∙+
∙+
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 180
C5H8N3
me 109
C5H7N3
me 109
C4H5N2
me 82
C4H5Nme 67
N
N
O
O
N
N
H
NO
N
N
H
minusHCNminusHCN
minusHNCON
N
O
N
N
NCH
NCH
CHCHN
N
N
N
H
(b)
(a)
Nme 55
NHC
NH
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3CH3 ∙+
∙
∙
∙
∙+
∙+
N
N
N
minusCO
C6H7N3O∙+
me 137
O+
C+
+N
N
O
O
N
N
H
Sn
N
N
O
O
N
N
H
N
N
O
O
N
N
H
R R
RCl
Cl
Cl
R R
R
Sn
Sn
R R
R+
CH3
CH3
CH3
CH3
CH3
CH3∙+
∙+
∙+
C7H8N4O2
∙+
me 180
C7H8N4O2
me 180
Scheme 2 Fragmentation pattern for theobromine complexes
Journal of Chemistry 9
Table 4 Phenomenological data for the thermal decomposition of the complexes
Complex Step number TG plateaux (K) Mass loss Nature of lossObserved Calc
(C6H5CH2)3Sn(L1) I 483ndash673 460 4786 Loss of 3 benzyl groups
II 893ndash1003 720 7373 Formation of SnO2
(p-ClC6H4CH2)3Sn(L1) I 443ndash633 550 5580 Loss of 3 p-chlorobenzyl groups
II 873ndash973 750 7773 Formation of SnO2
(C6H5CH2)2Sn(L1)Cl
I 513ndash663 347 3536 Loss of 2 benzyl groupsII 703ndash773 420 4220 Loss of chlorine atomIII 893ndash973 694 7088 Formation of SnO2
(p-ClC6H4CH2)2Sn(L1)Cl
I 483ndash673 420 4294 Loss of 2 p-chlorobenzyl groupsII 723ndash793 470 4898 Loss of chlorine atomIII 873ndash973 735 7429 Formation of SnO2
(C6H5CH2)3Sn(L2)Cl
I 473ndash653 450 450 Loss of 3 benzyl groupsII 723ndash813 500 5080 Loss of chlorine atomIII 893ndash1003 740 7529 Formation of SnO2
(p-ClC6H4CH2)3Sn(L2)Cl
I 423ndash623 520 5295 Loss of 3 p-chlorobenzyl groupsII 703ndash753 570 5792 Loss of chlorine atomIII 873ndash973 780 7887 Formation of SnO2
(C6H5CH2)2Sn(L2)Cl2
I 493ndash653 320 3304 Loss of 2 benzyl groupsII 703ndash773 450 4582 Loss of chlorine atomsIII 873ndash993 710 7279 Formation of SnO2
(p-ClC6H4CH2)2Sn(L2)Cl2
I 473ndash653 400 4043 Loss of 2 p-chlorobenzyl groupsII 723ndash793 500 5180 Loss of chlorine atomsIII 873ndash973 750 7580 Formation of SnO2
for the thermal decomposition of the complexes are given inTable 5
On the basis of the above data it can be concludedthat the complexes with R = p-ClC
6H4CH2ndash have lower 119864
119886
value for step 1 as compared to the complexes with the samenumber of R groups but R = C
6H5CH2ndash because the electron
withdrawing effect of chlorine makes the RndashSn bond weakerand facilitates its thermal degradation Moreover tri(p-chlorobenzyl)tin derivative has the least activation energy forthe first step due to the greater steric hindrance
36 In Vitro Antibacterial Studies Themetal complexes werescreened versus Ecoli S aureus and P pyocyanea bacterialstrains using the respective ligands as the standard forcomparing the activities The samples were screened at threedifferent concentrations (25 50 and 100 120583g cmminus3) in DMFThe inhibitory power of the metal complexes was observedto be greater than that of the control The general orderof activity versus the three microorganisms is Saureus gt Ppyocyanea gt EcoliThe data is presented in Table 6
37 Antifungal Studies The results reported in Table 7 revealthat the organotin complexes with these ligands are muchmore active than the parent ligand against the same microor-ganisms With increase in concentration of the compoundsthere occurs increase in percentage of inhibition Higherconcentration proves inhibitory for fungal growth
Sn
Cl
ClCl
Cl
N
N
N
N
OH
OCH3
CH2
CH2
H3C
Figure 2
On the basis of spectral evidence Figure 2 representingcoordination has been prepared for one of the complexessynthesized
Conflict of Interests
The authors declare that they have no conflict of interests
10 Journal of Chemistry
Table5Kinetic
parametersfor
thetherm
aldecompo
sitionof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Step
number
TempK
Coats-
Redfernmetho
dHorow
itz-M
etzger
metho
dDTA
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
Thermaleffect
Δ119867
(Jgminus
1 )
(C6H
5CH
2)3Sn(L1)
1483ndash673
5109
941
5423
1046
Exo
minus2042
2893ndash1003
30635
3762
31017
3801
Endo
9446
(p-C
lC6H
4CH
2)3Sn(L1)
144
3ndash633
4030
850
4184
881
Exo
minus1746
2873ndash973
21882
2742
24323
2982
Endo
9326
(C6H
5CH
2)2Sn(L1)C
l1
513ndash663
6382
1200
6562
1233
Exo
minus2210
2703ndash773
1915
43206
2114
03326
Exo
minus8999
3893ndash973
36698
4541
35353
443
Endo
9042
(p-C
lC6H
4CH
2)2Sn(L1)C
l1
483ndash673
5470
1054
5523
1067
Exo
minus2169
2723ndash793
25529
3942
23849
3764
Exo
minus9246
3873ndash973
38294
4745
38048
4785
Endo
9291
(C6H
5CH
2)3Sn(L2)C
l1
473ndash653
3829
697
4046
795
Exo
minus3046
2723ndash813
8703
1206
9534
1383
Exo
minus5249
3893ndash1003
20812
2410
21731
2622
Endo
11112
(p-C
lC6H
4CH
2)3Sn(L2)C
l1
423ndash623
3191
620
3491
741
Exo
minus2962
2703ndash753
25529
4162
25021
4069
Exo
minus5162
3873ndash973
2393
33041
25095
3189
Endo
11342
(C6H
5CH
2)2Sn(L2)C
l 21
493ndash653
5744
1120
5855
1135
Exo
minus2994
2703ndash773
2815
74369
27433
4344
Exo
minus5160
3873ndash993
17632
2142
17857
2157
Endo
11021
(p-C
lC6H
4CH
2)2Sn(L2)C
l 21
473ndash653
5444
784
5645
826
Exo
minus3106
2723ndash793
1914
72947
19218
2971
Exo
minus5206
3873ndash973
23753
2901
24328
2999
Endo
11226
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
8 Journal of Chemistry
+
+
N
N
O
O
N
N
H
N
N
O
O
N
N
H
Cl
N
N
O
O
N
N
H
R R
R
Sn
Sn
R R
Cl R
CH3
CH3
CH3
CH3CH3
CH3
∙+
∙+
∙+
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 18006
C7H8N4O2
∙+
me 180
C5H8N3
me 109
C5H7N3
me 109
C4H5N2
me 82
C4H5Nme 67
N
N
O
O
N
N
H
NO
N
N
H
minusHCNminusHCN
minusHNCON
N
O
N
N
NCH
NCH
CHCHN
N
N
N
H
(b)
(a)
Nme 55
NHC
NH
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3
CH3CH3 ∙+
∙
∙
∙
∙+
∙+
N
N
N
minusCO
C6H7N3O∙+
me 137
O+
C+
+N
N
O
O
N
N
H
Sn
N
N
O
O
N
N
H
N
N
O
O
N
N
H
R R
RCl
Cl
Cl
R R
R
Sn
Sn
R R
R+
CH3
CH3
CH3
CH3
CH3
CH3∙+
∙+
∙+
C7H8N4O2
∙+
me 180
C7H8N4O2
me 180
Scheme 2 Fragmentation pattern for theobromine complexes
Journal of Chemistry 9
Table 4 Phenomenological data for the thermal decomposition of the complexes
Complex Step number TG plateaux (K) Mass loss Nature of lossObserved Calc
(C6H5CH2)3Sn(L1) I 483ndash673 460 4786 Loss of 3 benzyl groups
II 893ndash1003 720 7373 Formation of SnO2
(p-ClC6H4CH2)3Sn(L1) I 443ndash633 550 5580 Loss of 3 p-chlorobenzyl groups
II 873ndash973 750 7773 Formation of SnO2
(C6H5CH2)2Sn(L1)Cl
I 513ndash663 347 3536 Loss of 2 benzyl groupsII 703ndash773 420 4220 Loss of chlorine atomIII 893ndash973 694 7088 Formation of SnO2
(p-ClC6H4CH2)2Sn(L1)Cl
I 483ndash673 420 4294 Loss of 2 p-chlorobenzyl groupsII 723ndash793 470 4898 Loss of chlorine atomIII 873ndash973 735 7429 Formation of SnO2
(C6H5CH2)3Sn(L2)Cl
I 473ndash653 450 450 Loss of 3 benzyl groupsII 723ndash813 500 5080 Loss of chlorine atomIII 893ndash1003 740 7529 Formation of SnO2
(p-ClC6H4CH2)3Sn(L2)Cl
I 423ndash623 520 5295 Loss of 3 p-chlorobenzyl groupsII 703ndash753 570 5792 Loss of chlorine atomIII 873ndash973 780 7887 Formation of SnO2
(C6H5CH2)2Sn(L2)Cl2
I 493ndash653 320 3304 Loss of 2 benzyl groupsII 703ndash773 450 4582 Loss of chlorine atomsIII 873ndash993 710 7279 Formation of SnO2
(p-ClC6H4CH2)2Sn(L2)Cl2
I 473ndash653 400 4043 Loss of 2 p-chlorobenzyl groupsII 723ndash793 500 5180 Loss of chlorine atomsIII 873ndash973 750 7580 Formation of SnO2
for the thermal decomposition of the complexes are given inTable 5
On the basis of the above data it can be concludedthat the complexes with R = p-ClC
6H4CH2ndash have lower 119864
119886
value for step 1 as compared to the complexes with the samenumber of R groups but R = C
6H5CH2ndash because the electron
withdrawing effect of chlorine makes the RndashSn bond weakerand facilitates its thermal degradation Moreover tri(p-chlorobenzyl)tin derivative has the least activation energy forthe first step due to the greater steric hindrance
36 In Vitro Antibacterial Studies Themetal complexes werescreened versus Ecoli S aureus and P pyocyanea bacterialstrains using the respective ligands as the standard forcomparing the activities The samples were screened at threedifferent concentrations (25 50 and 100 120583g cmminus3) in DMFThe inhibitory power of the metal complexes was observedto be greater than that of the control The general orderof activity versus the three microorganisms is Saureus gt Ppyocyanea gt EcoliThe data is presented in Table 6
37 Antifungal Studies The results reported in Table 7 revealthat the organotin complexes with these ligands are muchmore active than the parent ligand against the same microor-ganisms With increase in concentration of the compoundsthere occurs increase in percentage of inhibition Higherconcentration proves inhibitory for fungal growth
Sn
Cl
ClCl
Cl
N
N
N
N
OH
OCH3
CH2
CH2
H3C
Figure 2
On the basis of spectral evidence Figure 2 representingcoordination has been prepared for one of the complexessynthesized
Conflict of Interests
The authors declare that they have no conflict of interests
10 Journal of Chemistry
Table5Kinetic
parametersfor
thetherm
aldecompo
sitionof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Step
number
TempK
Coats-
Redfernmetho
dHorow
itz-M
etzger
metho
dDTA
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
Thermaleffect
Δ119867
(Jgminus
1 )
(C6H
5CH
2)3Sn(L1)
1483ndash673
5109
941
5423
1046
Exo
minus2042
2893ndash1003
30635
3762
31017
3801
Endo
9446
(p-C
lC6H
4CH
2)3Sn(L1)
144
3ndash633
4030
850
4184
881
Exo
minus1746
2873ndash973
21882
2742
24323
2982
Endo
9326
(C6H
5CH
2)2Sn(L1)C
l1
513ndash663
6382
1200
6562
1233
Exo
minus2210
2703ndash773
1915
43206
2114
03326
Exo
minus8999
3893ndash973
36698
4541
35353
443
Endo
9042
(p-C
lC6H
4CH
2)2Sn(L1)C
l1
483ndash673
5470
1054
5523
1067
Exo
minus2169
2723ndash793
25529
3942
23849
3764
Exo
minus9246
3873ndash973
38294
4745
38048
4785
Endo
9291
(C6H
5CH
2)3Sn(L2)C
l1
473ndash653
3829
697
4046
795
Exo
minus3046
2723ndash813
8703
1206
9534
1383
Exo
minus5249
3893ndash1003
20812
2410
21731
2622
Endo
11112
(p-C
lC6H
4CH
2)3Sn(L2)C
l1
423ndash623
3191
620
3491
741
Exo
minus2962
2703ndash753
25529
4162
25021
4069
Exo
minus5162
3873ndash973
2393
33041
25095
3189
Endo
11342
(C6H
5CH
2)2Sn(L2)C
l 21
493ndash653
5744
1120
5855
1135
Exo
minus2994
2703ndash773
2815
74369
27433
4344
Exo
minus5160
3873ndash993
17632
2142
17857
2157
Endo
11021
(p-C
lC6H
4CH
2)2Sn(L2)C
l 21
473ndash653
5444
784
5645
826
Exo
minus3106
2723ndash793
1914
72947
19218
2971
Exo
minus5206
3873ndash973
23753
2901
24328
2999
Endo
11226
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 9
Table 4 Phenomenological data for the thermal decomposition of the complexes
Complex Step number TG plateaux (K) Mass loss Nature of lossObserved Calc
(C6H5CH2)3Sn(L1) I 483ndash673 460 4786 Loss of 3 benzyl groups
II 893ndash1003 720 7373 Formation of SnO2
(p-ClC6H4CH2)3Sn(L1) I 443ndash633 550 5580 Loss of 3 p-chlorobenzyl groups
II 873ndash973 750 7773 Formation of SnO2
(C6H5CH2)2Sn(L1)Cl
I 513ndash663 347 3536 Loss of 2 benzyl groupsII 703ndash773 420 4220 Loss of chlorine atomIII 893ndash973 694 7088 Formation of SnO2
(p-ClC6H4CH2)2Sn(L1)Cl
I 483ndash673 420 4294 Loss of 2 p-chlorobenzyl groupsII 723ndash793 470 4898 Loss of chlorine atomIII 873ndash973 735 7429 Formation of SnO2
(C6H5CH2)3Sn(L2)Cl
I 473ndash653 450 450 Loss of 3 benzyl groupsII 723ndash813 500 5080 Loss of chlorine atomIII 893ndash1003 740 7529 Formation of SnO2
(p-ClC6H4CH2)3Sn(L2)Cl
I 423ndash623 520 5295 Loss of 3 p-chlorobenzyl groupsII 703ndash753 570 5792 Loss of chlorine atomIII 873ndash973 780 7887 Formation of SnO2
(C6H5CH2)2Sn(L2)Cl2
I 493ndash653 320 3304 Loss of 2 benzyl groupsII 703ndash773 450 4582 Loss of chlorine atomsIII 873ndash993 710 7279 Formation of SnO2
(p-ClC6H4CH2)2Sn(L2)Cl2
I 473ndash653 400 4043 Loss of 2 p-chlorobenzyl groupsII 723ndash793 500 5180 Loss of chlorine atomsIII 873ndash973 750 7580 Formation of SnO2
for the thermal decomposition of the complexes are given inTable 5
On the basis of the above data it can be concludedthat the complexes with R = p-ClC
6H4CH2ndash have lower 119864
119886
value for step 1 as compared to the complexes with the samenumber of R groups but R = C
6H5CH2ndash because the electron
withdrawing effect of chlorine makes the RndashSn bond weakerand facilitates its thermal degradation Moreover tri(p-chlorobenzyl)tin derivative has the least activation energy forthe first step due to the greater steric hindrance
36 In Vitro Antibacterial Studies Themetal complexes werescreened versus Ecoli S aureus and P pyocyanea bacterialstrains using the respective ligands as the standard forcomparing the activities The samples were screened at threedifferent concentrations (25 50 and 100 120583g cmminus3) in DMFThe inhibitory power of the metal complexes was observedto be greater than that of the control The general orderof activity versus the three microorganisms is Saureus gt Ppyocyanea gt EcoliThe data is presented in Table 6
37 Antifungal Studies The results reported in Table 7 revealthat the organotin complexes with these ligands are muchmore active than the parent ligand against the same microor-ganisms With increase in concentration of the compoundsthere occurs increase in percentage of inhibition Higherconcentration proves inhibitory for fungal growth
Sn
Cl
ClCl
Cl
N
N
N
N
OH
OCH3
CH2
CH2
H3C
Figure 2
On the basis of spectral evidence Figure 2 representingcoordination has been prepared for one of the complexessynthesized
Conflict of Interests
The authors declare that they have no conflict of interests
10 Journal of Chemistry
Table5Kinetic
parametersfor
thetherm
aldecompo
sitionof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Step
number
TempK
Coats-
Redfernmetho
dHorow
itz-M
etzger
metho
dDTA
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
Thermaleffect
Δ119867
(Jgminus
1 )
(C6H
5CH
2)3Sn(L1)
1483ndash673
5109
941
5423
1046
Exo
minus2042
2893ndash1003
30635
3762
31017
3801
Endo
9446
(p-C
lC6H
4CH
2)3Sn(L1)
144
3ndash633
4030
850
4184
881
Exo
minus1746
2873ndash973
21882
2742
24323
2982
Endo
9326
(C6H
5CH
2)2Sn(L1)C
l1
513ndash663
6382
1200
6562
1233
Exo
minus2210
2703ndash773
1915
43206
2114
03326
Exo
minus8999
3893ndash973
36698
4541
35353
443
Endo
9042
(p-C
lC6H
4CH
2)2Sn(L1)C
l1
483ndash673
5470
1054
5523
1067
Exo
minus2169
2723ndash793
25529
3942
23849
3764
Exo
minus9246
3873ndash973
38294
4745
38048
4785
Endo
9291
(C6H
5CH
2)3Sn(L2)C
l1
473ndash653
3829
697
4046
795
Exo
minus3046
2723ndash813
8703
1206
9534
1383
Exo
minus5249
3893ndash1003
20812
2410
21731
2622
Endo
11112
(p-C
lC6H
4CH
2)3Sn(L2)C
l1
423ndash623
3191
620
3491
741
Exo
minus2962
2703ndash753
25529
4162
25021
4069
Exo
minus5162
3873ndash973
2393
33041
25095
3189
Endo
11342
(C6H
5CH
2)2Sn(L2)C
l 21
493ndash653
5744
1120
5855
1135
Exo
minus2994
2703ndash773
2815
74369
27433
4344
Exo
minus5160
3873ndash993
17632
2142
17857
2157
Endo
11021
(p-C
lC6H
4CH
2)2Sn(L2)C
l 21
473ndash653
5444
784
5645
826
Exo
minus3106
2723ndash793
1914
72947
19218
2971
Exo
minus5206
3873ndash973
23753
2901
24328
2999
Endo
11226
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
10 Journal of Chemistry
Table5Kinetic
parametersfor
thetherm
aldecompo
sitionof
theoph
yllin
eand
theobrom
inec
omplexes
Com
plex
Step
number
TempK
Coats-
Redfernmetho
dHorow
itz-M
etzger
metho
dDTA
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
119864119886kJm
olminus1Δ119878(JKminus
1 molminus1 )
Thermaleffect
Δ119867
(Jgminus
1 )
(C6H
5CH
2)3Sn(L1)
1483ndash673
5109
941
5423
1046
Exo
minus2042
2893ndash1003
30635
3762
31017
3801
Endo
9446
(p-C
lC6H
4CH
2)3Sn(L1)
144
3ndash633
4030
850
4184
881
Exo
minus1746
2873ndash973
21882
2742
24323
2982
Endo
9326
(C6H
5CH
2)2Sn(L1)C
l1
513ndash663
6382
1200
6562
1233
Exo
minus2210
2703ndash773
1915
43206
2114
03326
Exo
minus8999
3893ndash973
36698
4541
35353
443
Endo
9042
(p-C
lC6H
4CH
2)2Sn(L1)C
l1
483ndash673
5470
1054
5523
1067
Exo
minus2169
2723ndash793
25529
3942
23849
3764
Exo
minus9246
3873ndash973
38294
4745
38048
4785
Endo
9291
(C6H
5CH
2)3Sn(L2)C
l1
473ndash653
3829
697
4046
795
Exo
minus3046
2723ndash813
8703
1206
9534
1383
Exo
minus5249
3893ndash1003
20812
2410
21731
2622
Endo
11112
(p-C
lC6H
4CH
2)3Sn(L2)C
l1
423ndash623
3191
620
3491
741
Exo
minus2962
2703ndash753
25529
4162
25021
4069
Exo
minus5162
3873ndash973
2393
33041
25095
3189
Endo
11342
(C6H
5CH
2)2Sn(L2)C
l 21
493ndash653
5744
1120
5855
1135
Exo
minus2994
2703ndash773
2815
74369
27433
4344
Exo
minus5160
3873ndash993
17632
2142
17857
2157
Endo
11021
(p-C
lC6H
4CH
2)2Sn(L2)C
l 21
473ndash653
5444
784
5645
826
Exo
minus3106
2723ndash793
1914
72947
19218
2971
Exo
minus5206
3873ndash973
23753
2901
24328
2999
Endo
11226
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 11
Table 6 Antibacterial activity of theophylline and theobromine complexes
CompoundDiameter of inhibition zone (mm) after 24 hr
Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000
HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L
1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L
1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L
1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L
1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L
2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L
2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L
2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L
2)Cl2 10 11 12 16 10 14 11 13
Table 7 Antifungal activity of theophylline and theobromine complexes
CompoundAverage inhibition after 96H
Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)
HL1 33 42 39 48(C6H5CH2)3Sn(L
1) 60 79 63 77(p-ClC6H4CH2)3Sn(L
1) 55 61 65 79(C6H5CH2)2Sn(L
1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L
1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L
2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L
2)Cl 52 64 58 73(C6H5CH2)2Sn(L
2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L
2)Cl2 62 73 68 82Bavistin 82 96 84 98
References
[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002
[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010
[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994
[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004
[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004
[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998
[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008
[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009
[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009
[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006
[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
12 Journal of Chemistry
[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008
[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005
[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995
[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006
[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006
[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002
[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)
2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-
OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008
[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003
[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003
[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995
[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003
[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992
[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002
[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985
[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971
[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970
[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950
[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945
[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984
[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961
[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987
[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984
[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989
[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978
[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964
[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963
[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968
[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969
[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
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