Ligational, Spectroscopic (Infrared and Electronic) and...

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Borderless Science Publishing 24

Canadian Chemical Transactions Year 2014 | Volume 2 | Issue 1| Page 24-35

ISSN 2291-6458 (Print), ISSN 2291-6466 (Online)

Research Article DOI:10.13179/canchemtrans.2014.02.01.0062

Ligational, Spectroscopic (Infrared and Electronic) and

Thermal Studies on the Mn(II), Co(II), Fe(II) and Cu(II)

Complexes with Analgesic Drugs

Moamen S. Refat

1,2*, Sabry A. El-Korashy

3 and Mostafa A. Hussien

1

1 Chemistry Department, Faculty of Science, Port-Said University, Port-Said, Egypt

2 Chemistry Department, Faculty of Science, Taif, Taif University, 888 Taif, Kingdom Saudi Arabia

3 Chemistry Department, Faculty of Science, Suez Canal University, Ismailia, Egypt

*Corresponding Author, E-mail: [email protected]

Received: November11, 2013 Revised: December 1, 2013 Accepted: December2, 2013 Published: December 3, 2013

Abstract: The goal of this paper is to get a wide understanding of the structural and spectral properties as

well as microbial activities of ibuprofen and paracetamol and their Mn(II), Co(II), Fe(II) and Cu(II) metal

ion complexes. Metallo-ibuprofen/paracetamol complexes were investigated by spectral and thermal

techniques. The IR spectral data suggested that the paracetamol ligand behaves as a neutral bi-dentate

ligand coordinated to the metal ions via the lone pair of electrons of nitrogen and carbonyl-O atoms of the

amide group. On the other hand, ibuprofen liganed behaves as a monobasic bi-dentate ligand coordinated

to the metal ions via the deprotonated carboxylate O atom. From the micro-analytical data, the

stoichiometry of the complexes reacts with Mn(II), Co(II), Fe(II) and Cu(II) by molar ratios (2:1)

(drug:metal ion). The thermal behavior (TG/DTG) of the complexes was studied.

Keywords: Paracetamol; Ibuprofen; Transition Metal; Thermal Analysis; Antimicrobial Activity

1. INTRODUCTION

A number of drugs and potential pharmaceutical agents also contain metal-binding or metal-

recognition sites, which can bind or interact with metal ions and potentially influence their bioactivities,

and might also cause damages on their target biomolecules. Numerous examples these ‘‘metallodrugs’’

and ‘‘metallopharmaceuticals’’ and their actions can be found in the literature, for instance: (a) several

anti-inflammatory drugs, such as aspirin and its metabolite salicylglycine [1-4], suprofen [5], are known

to bind metal ions and affect their antioxidant and anti-inflammatory activities; (b) the potent histamine-

H2-receptor antagonist cimetidine [6] can form complexes with Cu‏+2

and Fe and the histidine blocker ,‏+3

antiulcer drug famotidine can also form stable complex with Cu the anthelmintic and (c) ,[7,8] ‏+2

fungistatic agent thiabendazole, which is used for the treatment of several parasitic diseases, forms a Co+‏2

complex with metal:drug ratio of 1:2 [9] (d) the Ru complex of the anti-malaria agent chloroquine ‏+2

exhibits an activity two to five times higher than the parent drug against drug-resistant strains of

Plasmodium faciparum [10].

mailto:[email protected]

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Canadian Chemical Transactions Year 2014 | Volume 2 | Issue 1| 4-35


Figure 1. Structure of Ibuprofen and Paracetamol

O

O

O

O

O

O

OO

Fe

Fe

OH2

H2O

O

O

O

O

O

O

OO

Cu

Cu

OH2

H2O

O

O

O

O

O

O

OO

Co

Co

OH2

H2O

O

O

O

O

O

O

OO

Mn

Mn

OH2

H2O

Figure 2. Structure of the Ibuprofen complexes

An analgesic is any member of the group of drugs used to relieve pain (achieve analgesia).

Analgesic drugs act in various ways on the peripheral and central nervous systems, they include

paracetamol (para-acetylaminophenol, also known in the US as acetaminophen), the non-steroidal anti-

inflammatory drugs (NSAIDs) such as the salicylates, narcotic drugs such as morphine, synthetic drugs

with narcotic properties such as tramadol. Complexes of ketoprofen, another NSAID, with lighter and

heavier lanthanides were synthesized and characterized [11, 12]. The motivation for the preparation of

lanthanide complexes with NSAIDs is the structural similarity with other lanthanide complexes already

http://en.wikipedia.org/wiki/Medication

http://en.wikipedia.org/wiki/Pain

http://en.wikipedia.org/wiki/Peripheral_nervous_system

http://en.wikipedia.org/wiki/Central_nervous_system

http://en.wikipedia.org/wiki/Narcotic

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reported in the literature that showed pharmacological, diagnostic and therapeutic applications [13].

[Ru2(dNSAID)4Cl] and novel [Ru2(dNSAID)4(H2O)2]PF6 complexes, where dNSAID =

deprotonated carboxylate from the non-steroidal anti-inflammatory drugs (NSAIDs), respectively:

ibuprofen, aspirin, naproxen and indomethacin, have been prepared and characterized by optical

spectroscopic methods. All of the compounds exhibit mixed valent Ru2(II, III) cores where metal–metal

bonds are stabilized by four drug-carboxylate bridging ligands in paddlewheel type structures [14]. Three

new vanadyl(IV) complexes with non-steroidal anti-inflammatory drugs, ibuprofen, naproxen, and

tolmetin, were synthesized and characterized by means of elemental analysis, UV–vis, diffuse reflectance

and IR spectroscopies as well as their magnetic behavior [15]. The biological activity of these vanadium

compounds was tested on two osteoblast-like cells in culture through a proliferation bioassay. Complexes

of Zn(II), Cd(II) and Pt(II) metal ions with the anti-inflammatory drugs, tolmetin, ibuprofen, naproxen

and indomethacin have been synthesized and characterized [16]. The kinetics of the oxidation of

ruthenium(III)- and osmium(VIII)-catalysed oxidation of paracetamol by diperiodatoargentate(III) (DPA)

in aqueous alkaline medium at a constant ionic strength of 0.10 mol dm-3

was studied

spectrophotometrically [17]. The reaction between DPA and paracetamol in alkaline medium exhibits 2:1

stoichiometry in both catalysed reactions (DPA:Par). The main products were identified by spot test, IR,

NMR and GC–MS. Probable mechanisms are proposed and discussed. The activation parameters with

respect to the slow step of the mechanism are computed and discussed and thermodynamic quantities are

also calculated.

In this paper the complexes of Mn(II), Co(II), Fe(II) and Cu(II) with ibuprofen or paracetamol

drug were synthesized and characterized by elemental analysis, conductivity, UV–Vis, IR spectroscopy

and thermal analysis, as well as screened for antimicrobial activity.

2. EXPERIMENTAL

2.1 Materials

All chemicals used were of the purest laboratory grade Merck and both of ibuprofen and

paracetamol (Fig. 1) were presented from Egyptian international pharmaceutical industrial company

(EIPICo.).

2.2 Preparation of solid complexes

For all preparations, doubly distilled water employed as solvent. All used reagents were of

analytical grade and employed without further purifications. Cu(II) chloride, Fe(II) chloride, Mn(II)

chloride and Co(II) chloride (1 mmol, Fluka) were dissolved in 20 cm3 of water and then the prepared

solutions were slowly added to 25 cm3 of an aqueous solution with 1 mmol of ligand solution under

magnetic stirring. The pH of each solution adjusted to 6-8 by addition of ammonium hydroxide. The

resulting solutions heated at 50 oC and left to evaporate slowly at room temperature overnight. The

obtained precipitates were filtered-off, wash with hot water and then dried at 60 oC.

2. 3 Micro-analytical and instrumental techniques

Carbon and hydrogen contents were determined using a Perkin-Elmer CHN 2400. The metal

content found gravimetrically by converting the compounds into their corresponding oxides. The sulfate

content in the sulfate containing complexes was determined gravimetrically as barium sulphate using

BaCl2 solution as a precipitating agent. Chloride content in all prepared complexes determined

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Figure 3. Structure of the paracetamol complexes

potentiometrically by the titration against a standard AgNO3 Materials. Mn(II), Co(II), Fe(III)

and Cu(II) were determined atomic absorption technique. Molar conductivities of freshly prepared

1.0×10-3

mol/dm-3

dimethylsulfoxide ‘DMSO’ solutions measured using Jenway 4010 conductivity meter.

IR spectra were recorded on Bruker FTIR Spectrophotometer (4000–400 cm-1

) in KBr pellets. The UV–

vis, spectra were determined in the DMSO solvent with concentration (1.0×10-3

M) for the free ligands

and their complexes using Jenway 6405 Spectrophotometer with 1cm quartz cell, in the range 200–800

nm. Thermogravimetric analyses (TG) carried out in the temperature range from 25 to 800 oC in a steam

of nitrogen atmosphere by Shimadzu TGA 50H thermal analysis. The experimental conditions were:

platinum crucible, nitrogen atmosphere with a 30 ml/min flow rate and a heating rate of 10 oC/min.

2. 4 Microbiological investigation

The investigated isolates of bacteria were seeded in tubes with nutrient broth (NB). The seeded

NB (1 cm3) was homogenized in the tubes with 9 cm

3 of melted (45

oC) nutrient agar (NA). The

homogeneous suspensions were poured into Petri dishes. The discs of filter paper (diameter 4 mm) were

ranged on the cool medium. After cooling on the formed solid medium, 2×10-5

dm3 of the investigated

compounds were applied using a micropipette. After incubation for 24 h in a thermostat at 25–27 oC, the

inhibition (sterile) zone diameters (including disc) were measured and expressed in mm. An inhibition

zone diameter over 7 mm indicates that the tested compound is active against the bacteria under

investigation [18]. The antibacterial activities of the investigated compounds were tested against

Escherichia Coli (Gram -ve), Bacillus subtilis (Gram +ve) and antifungal (tricoderma and penicillium).

The concentration of each solution was 1.0×10-3

mol dm3. Commercial DMSO was employed to dissolve

the tested samples.

3. RESULTS AND DISCUSSION

3.1. Elemental analyses and conductivity data

The elemental analysis results were summarized in Tables 1 and 2. These results were in good

agreement with the proposed formulae’s. The melting points of the ibuprofen and paracetamol complexes

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Table 1. Analytical and physical data of Ibu and its metal complexes

Complex

Mwt Formula %C %H

Calc. Found Calc. Found

Mn2(Ibu)4(H2O)2 969.01 C52H74Mn2O10 64.45 64.57 7.70 7.66

Co2(Ibu)4(H2O)2 974.99 C52H74Co2O10 64.06 64.28 7.44 7.43

Fe2(Ibu)4(H2O)2 968.81 C52H74Fe2O10 64.47 64.48 7.49 7.55

Cu(Ibu)2(H2O)2 986.23 C52H74Cu2O10 63.33 63.43 7.56 7.59

Table 2. Analytical and physical data of Par and its metal complexes

Complex

Mwt Formula %C %H %N

Calc. Found Calc. Found Calc. Found

Mn(Par)2 355.25 C16H16MnN2O4 54.10 54.32 4.54 4.67 7.89 7.18

Co(Par)2 359.24 C16H16CoN2O4 53.49 54.01 4.49 4.86 7.80 7.66

Fe(Par)2(OH)(H2O) 406.17 C16H18FeN2O7 47.31 47.44 4.47 4.60 6.90 6.98

Cr(Par)2 (OH)(H2O) 402.32 C16H18CrN2O7 47.77 47.78 4.51 4.54 6.96 6.72

Table 3. IR spectra (4000-400 cm-1

) of Ibu and its metal complexes

Table 4. IR spectra (4000-400 cm

-1) of Paracetamol and its metal complexes

were higher than that of the free ligand, revealing that the complexes are much more stable than

ligand. The molar conductivity values for the ibuprofen complexes in DMSO solvent 1.00×10-3

mol were

in the range 6.50-44.40 Ω-1

cm-1

mol-1

, suggesting them to be non-electrolytes nature. Conductivity

measurements have frequently used in elucidation of structure of metal chelates (mode of coordination)

within the limits of their solubility. They provide a method of testing the degree of ionization of the

complexes, the molecular ions that a complex liberates in solution in case of presence of anions outside

the coordination sphere, the higher will be its molar conductivity and vice versa [19]. It was clear from

the conductivity data that the complexes present seem to be non-electrolytes. Paracetamol complexes

have conductance values in the range from 53-to-84 Ω-1

cm2mol

-1 at 25

oC, which indicates that the

complexes were of a non-electrolytic nature. The low conductivity values were in agreement with the low

Compound (COO)

(sym)

v(COO)

(asym.)

∆

v(M-O)

(COO) (M-O)

(H2O)

Ibuprofen 11594sh 1413sh 141 --- ---

Mn2(Ibu)4(H2O)2 1565s 1410m 154 417s 560s

Co2(Ibu)4(H2O)2 1578m 1403s 175 403w 556s

Fe2(Ibu)4(H2O)2 1592m 1403sh 189 419s 578s

Cu(Ibu)2(H2O)2 1555m 1402m 153 419w 558s

Compound v(NH) + ν(OH) ν(C=O) δ(CNH)

amide group

v(C-OH) v(M-O) (M-O) (M-O)

(H2O)

Paracetamol 3300 s 1640 vs 1540 (sh) s 1256 vs -- -- --

Mn(Par)2 3326 1655 1564 1255 489s 473s 543s

Co(Par)2 3325 1656 1562 1256 496w 466w 537s

Fe(Par)2(OH)(H2O) 3325 1654 1563 1256 496s 477w 517s

Cr(Par)2 (OH)(H2O) 3409 1623 1564 1255 486w 468w 528s

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solubility of parcetamol complexes in water, ethanol, chloroform, acetone and most organic solvents. On

the other hand, they were soluble in DMSO, dimethylformamide ‘DMF’ and concentrated acids.

3.2 Infrared spectral data

The IR spectra of the ibuprofen complexes were exhibit the characteristic pattern of the ligand

vibrational modes, which were very similar to those of the Na salts. But some notable differences can

observed in the 3500–3200 cm-1

, 1650–1300 cm-1

, and the low frequency ν(500 cm-1

) spectral regions. In

the 3500–3200 cm-1

. In the IR spectral region of metal complexes, the bands attributable to v(OH) were

broader and their intensity was weaker than that of the corresponding Na salts. This indicates that the

Metal ion coordinates fewer water molecules than the Na ion. In the 1650–1300 cm-1

spectral region the

stretching vibrations of the carboxylate ion (vas and vs) were present; these frequencies, as well as ∆v=vas -

vs, can give indications about the coordination modalities. Indeed, for metal complexes two main

structures were possible, a chelating bidentate and a bridged bidentate structure. Literature data obtained

by IR spectra of metal transition complexes with carboxylic acids with known structures (by X-ray

measurements) assign ∆v= 160 cm-1

for the bridging bidentate complexes, while chelating bidentate

complexes usually have ∆v <130 cm-1

[20]. Also, the values of vas and vs frequencies were indicative of

the complex structure, it has been reported that vas < 1570 cm-1

and vs < 1450 cm-1

were observed for the

bidentate chelate complexes of metal transition ions. The bridging bidentate complexes characterized by

vas < 1570 cm-1

[20] and vs <1400 cm-1

, Table 3, shows the IR spectra data of the metal complexes, their

vas and vs wavenumbers, and the corresponding ∆v values: in most cases, there was an Increase in both v

as and v s in comparison with the corresponding Na salt (Table 3). Moreover, the ∆ as increase was higher

than that of v s going from Na salts to metal complexes. The fact that vas was higher than the

corresponding frequencies of Na salts was in agreement with a binuclear diametric structure for the

complex [20].

From the comparative IR spectra of paracetamol and its complexes (Table 4), it has been noticed

a slight blue shift of the stretching band of the carbonyl group at 1640 cm−1

in paracetamol IR spectrum to

1654 cm−1

in the complexes spectra. A slight red shift of the in-plane bending band of the carbonyl group

of the paracetamol spectrum at 840–830 cm−1

in the complexes spectra and the disappearance of the in-

plane bending bands of CNH at the positions at 1540 cm−1

and 1260 cm−1

[20] in the IR spectra of the

complexes in addition to the disappearance or the intensity change of the out-of-plane wagging band of

NH in the amide group at 720 cm−1

in the complexes spectra. The appearance of the stretching band and

the in-plane bending band of the hydroxyl group, with respect to the phenyl moiety at positions 1240 cm−1

and 620 cm−1

[20] , respectively, excludes the contribution of the hydroxyl oxygen atom to be chelated

with the metal ion as well as the appearance of the stretching band in the hydroxyl group between oxygen

and hydrogen atom at position 3300 cm−1

verifies the assumption of exclusion of the hydroxyl oxygen

atom to be chelated with the metal ion in the complex.

3.3 Electronic spectral data

The electronic absorption spectra of the ligand and its M(ІІ) complexes in DMSO in the 200-600

nm range. It can see that free ibuprofen has two distinct absorption bands. The first one at 225 nm may be

attributed to π→π* transition of the heterocyclic moiety and benzene ring. The second band observed at

320 nm was attributed to n→π* electronic transition. It can see that free paracetamol has two distinct

absorption bands. The first one at 300 nm may be attributed to π→π* transition of the heterocyclic moiety

and benzene ring. The second band observed at 390 nm was attributed to n→π* electronic transition.

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Table 5. Thermodynamic data of the thermal decomposition of Ibu metal complexes

Complex TG range

(C)

DTGmax

(C)

Mass loss Total mass

% Found (Calcd.)

Assignment Residue

Mn2(Ibu)4(H2O)2 140-450 300 70.25(70.26) 64.65 (64.22) 2H2O+4C6H6 +6C2H2+4CO2 MnO

Co2(Ibu)4(H2O)2 140-450 300 54.60 (53.69) 45.49 (45.78) 2H2O+4C6H6+4C2H2+4CO2 CoO

Fe2(Ibu)4(H2O)2 140-450 300 70.03(70.12) 55.63 (55.63) 2H2O+4C6H6+6C2H2+4CO2 FeO

Cu(Ibu)2(H2O)2 140-450 300 69.02(69.57) 59.58 (59.21) 2H2O+4C6H6+6C2H2+4CO2 CuO

Table 6. Thermodynamic data of the thermal decomposition of Par metal complexes

Complex TG

range

(C)

DTGmax

(C)

Mass loss Total mass

% Found (Calcd.)

Assignment Metallic

residue

Mn(Par)2 30-340 300 89.34 (89.03) 19.89 (19.97) 2C6H6O+2H2O+ 2NO2 MnO

Co(Par)2

30-370

370-430

200

400

12.89 (12.81)

34.66 (34.53) 49.96 (50.94)

NO3

CH3OH+2NO2

CoO

Fe(Par)2(OH)(H2O)

30-220

220-400

100

300

8.90 (8.87)

39.53(39.41) 58.67 (58.10)

2H2O.

2H2O+2NO2+CH3OH

1/2Fe2O3

Cr(Par)2(OH)(H2O) 30-800 300 48.89 (51.26) 49.16 (48.74) 2C6H6O+H2O 1/2Cr2O3

# n = number of decomposition steps.

3.4 Mass spectral data

In the mass spectra of [Fe2(Ibu)4(H2O)2] intense mass peaks at m/z 206, 164, 107, 91 and 56

were detected. The first mass peak corresponds to the [H-Ibu]+ ion and the second one proceeds by

elimination of propane from the molecular ion at m/z 164, then the formation of 1-ethylbenzene ion at

m/z= 164. The molecular ion peak at m/z= 91 can be assigned to C7H7. In comparison between the

ibuprofen ligand and the Fe(III) complexes, the peak assigned to molecular ion m/z= 206 of ibuprofen

ligand was present complexe, and new peaks appear at m/z = 56 can be assigned to Fe(III). These results

were again consistent with the presence of direct metal-ligand bonding in the ibuprofen complexes. In the

mass spectrum of [Cr(Par)2(OH)(H2O)] intense mass peaks at m/z 151, 109, 80, 52 and 51 were detected.

The first mass peak corresponds to the [H-Par]+ ion and the second one proceeds by p-amino phenol from

the molecular ion at m/z 109 with intensity 75%, then the elimination of NO2 and OH groups leads to the

formation of Benzen ring ion at m/z= 79. In comparison between the paracetamol (ligand) and the Cr(III)

complexes, the peak assigned to molecular ion m/z= 151 of paracetamol ligand was present complexe,

and new peaks appear at m/z = 51 can be assigned to Cr(III). These results were again consistent with the

presence of direct metal-ligand bonding in the paracetamol complexes.

3.5 Thermal and kinetic studies

Thermal methods of analysis are widely used for checking thermal decomposition, thermal

stability [21–24], polymorphism [21], reactions in solid state, drug formulations [25–27], purity [28],

evolved gas analysis using simultaneous TG–FTIR [29] and other properties of solid compounds used in

pharmaceutical industry [30]. DSC was used as a screening technique to determine the compatibility of

ketoprofen with excipients [31], as well as theoretical calculations in structural investigations [23]. Owing

to the numerous issues involved, it becomes important to have a complete understanding of the properties

of pharmaceutical materials. The heating rates were controlled at 10 C min-1

under nitrogen atmosphere

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and the weight loss was measured from ambient temperature up to 1000 C. The data was listed in

Tables 5 and 6. The different thermodynamic parameters were calculated upon Coats-Redfern [32] and

Horowitz-Metzger [33] methods and listed in Tables 7 and 8.

3.5.1 Mn(II), Co(II), Fe(III) and Cu(II) Ibuprofen complexes

The thermal decomposition of Mn2(Ibu)4(H2O)2 occurs at one step. The degradation step takes

place in the range of 140-450 oC was corresponding to the loss of 2H2O, 4CO2, 6C2H2 and 4C6H6

molecules, representing a weight loss of 70.25 % and its calculated value was 70.26%.The MnO (polluted

with some carbon atoms) was the final product remains and was stable till 800 oC. The cobalt (II)

Ibuprofen complex decomposed in one-steps, occurring at 140-150 oC was corresponding to the loss of

2H2O, 4CO2, 6C2H2 and 4C6H6 molecules, representing a weight loss of 54.60 % and its calculated value

was 53.69%. The final products resulted at 800 oC contain CoO polluted with some carbon atoms. The

Fe(III) Ibuprofen complex decomposed in one steps, occurring at 140-450 oC was corresponding to the

loss of of 2H2O, 4CO2, 6C2H2 and 4C6H6 molecules, representing a weight loss of 70.03 % and its

calculated value was 70.12%. The final products resulted at 800 oC contain FeO polluted with some

carbon atoms. The thermal decomposition of Cu(Ibu)2(H2O)2 occurs in one steps. The degradation step

take place in the range of 140-450 o C and it was corresponds to the eliminated of 2H2O, 4CO2, 6C2H2 and

4C6H6 molecules due to a weight loss of 69.02% in a good matching with theoretical value 69.57%. The

CuO was the final product remains stable till 800 oC polluted with some carbon atoms. The data is

summarized in Table 7. The activation energies of decomposition found to be in the range 1.27 x104 - 9.70

x105 k J mol

-1. The high values of the activation energies reflect the thermal stability of the complexes.

The entropy of activation found to have negative values in all the complexes, which indicate that the

decomposition reactions proceed with a lower rate than the normal ones. On another meaning the thermal

decomposition process of all ibuprofen complexes were non-spontaneous, i.e, the complexes were

thermally stable. The correlation coefficients of the Arhenius plots of the thermal decomposition steps

found to lie in the range 0.9756 to 0.9991, showing a good fit with linear function.

3.5.2 Mn(II), Co(II), Fe(III) and Cu(II) paracetamol complexes

The weight losses for each paracetamol chelates calculated within the corresponding temperature

ranges (Table 6). The different thermodynamic parameters were listed in Table 8. The thermal

decomposition of Mn(Par)2 occurs in one step. The degradation step take place in the range of 30-340o C

and it was corresponds to the eliminated of 2 (C6H6O) +2H2O+ 2NO2 molecules due to a weight loss of

89.34 % in a good matching with theoretical value 89.03%. The MnO was the final product remains

stable till 800 oC. The cobalt(II) Paracetamol complex decomposed in two steps, the first one occurring at

30-370 oC and corresponding to the evolution of NO2, representing a weight loss of 12.89 % and its

calculated value was 12.81%. The second step occurring at 370-430 oC was corresponding to the loss of

CH3OH and 2NO2 molecules, representing a weight loss of 34.66 % and its calculated value was 34.53%.

The final products resulted at 900 oC contain CoO polluted with nine carbon atoms. The Fe(III)

paracetamol complex decomposed in two steps, the first one occurring at 30-220 oC and corresponding to

the evolution of 2H2O, representing a weight loss of 8.90% and its calculated value was 8.78%. The

second step occurring at 220-400 oC was corresponding to the loss of of 2H2O, 2NO2 and CH3OH

molecules, representing a weight loss of 39.53% and its calculated value was 39.41%. The final products

resulted at 900 oC contain Fe2O3 polluted with some carbon atoms. The thermal decomposition of

Cr(Par)2(OH)(H2O) occurs in one step. The degradation step take place in the range of 30-800 oC and it

was corresponds to the eliminated of (C6H6O)2 and H2O molecules due to a weight loss of 49.89 % in a

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Table 7: Thermodynamic data of the thermal decomposition of Ibu metal complexes

Complex Stage Method Parameter r

E

(kJ mol−1

)

A (s−1

) ΔS

(Jmol−1

K−1

)

ΔH

(kJmol−1

)

ΔG

(kJmol−1)

Ibu 1nd

CR

HM

average

1.72×104

1.41×104

1.57×104

4.25 ×105

7.07×105

5.66×105

-1.64 ×102

-1.53×102

-1.89×102

6.62×104

6.41×104

6.52×104

1.96×105

1.12×105

1.54×105

0.9947

0.9991

0.9969

Co 1st CR

HM

average

3.89×104

6.41×104

5.15×104

5.82 ×103

3.21×103

4.52×103

-1.50×102

-1.28×102

-1.39 ×102

5.52×104

5.14×104

5.33×104

1.72×105

1.59×105

1.66×105

0.9881

0.9895

0.9888

Cu 2st CR

HM

average

4.56 ×104

4.65×104

4.61×104

2.68×103

3.57×103

3.13×104

-1.72×102

-1.71×102

-1.72×102

2.47×104

3.69×104

3.08×104

1.14×105

1.93×105

1.55×105

0.9740

0.9771

0.9756

Fe

2nd

CR

HM

average

7.72×104

9.70×104

8.71×104

1.86×102

6.73 ×102

4.30×102

-2.93×102

-2.68×102

-2.81×102

3.21×104

1.25×104

2.23×104

1.54×105

1.52×105

1.54×105

0.9886

0.9961

0.9924

Mn 1st CR

HM

average

6.75×104

6.86×104

6.81×104

5.30×104

3.82×104

4.56×105

-1.60×102

-1.35×101

-1.48×102

5.14×104

5.74×104

5.44×104

1.70×105

1.67×105

1.69×105

0.9951

0.9959

0.9955

Table 8. Thermodynamic data of the thermal decomposition of Par metal complexes

Complex Stage Method Parameter r

E

(kJmol−1

)

A (s−1

) ΔS

(Jmol−1

K−1

)

ΔH

(kJmol−1

)

ΔG

(kJ mol−1)

Para 1st CR

HM

average

1.65×105

1.64×105

1.65 ×105

2.49×1012

1.47×1013

2.08×1013

-1.28×101

-1.01×101

-1.14 ×101

1.51×105

1.60×105

1.55×105

1.58×105

1.54×105

1.565×105

0.9998

0.9999

0.9999

Co

2nd

CR

HM

average

1.45×105

1.56×105

1.51×105

1.27×109

1.63×1010

8.79×109

-7.75×101

-6.00×101

-6.88 ×101

1.39×105

1.50×105

1.40×105

1.92×105

1.91×105

1.92×105

0.9984

0.9985

0.9985

Cr 2nd

CR

HM

average

7.40×104

5.31×104

6.36 ×104

1.71×105

3.05×106

1.61×105

-1.64×102

-1.22×102

-1.43 ×102

4.42×104

5.03×104

4.72×104

9.27×104

9.09×104

9.22×104

0.9916

0.9908

0.9912

Fe 1st CR

HM

average

4.84×104

5.19×104

5.06 ×104

7.44×105

7.33×106

4.04×106

-1.33×102

-1.14×102

-1.24 ×102

4.58×104

4.93×104

4.76×104

8.75×104

8.50×104

8.68×104

0.9899

0.9924

0.9912

Mn 1st CR

HM

average

1.25×105

1.35×105

1.30×105

8.39×108

1.37×1010

72.70×109

-7.97×101

-5.64×101

-6.80 ×101

11.2×105

1.30×105

1.25×105

1.67×105

1.63×105

1.67×105

0.9996

0.9997

0.9997

good matching with theoretical value 51.26%. The Cr2O3 was the final product remains stable

till 800 oC polluted with some carbon atoms. The data is summarized in Table 8, the activation energies of

decomposition found to be in the range 4.84x104-1.65x10

5 kJmol

-1. The high values of the activation

energies reflect the thermal stability of the complexes. The entropy of activation found to have negative

values in all the complexes, which indicate that the decomposition reactions proceed with a lower rate

than the normal ones. On another meaning the thermal decomposition process of all paracetamol

complexes were non-spontaneous, i.e, the complexes were thermally stable. The correlation coefficients

of the Arhenius plots of the thermal decomposition steps found to lie in the range 0.991 to 0.999, showing

Ca




a good fit with linear function.

3.6 Microbiological studies

Antibacterial and antifungal activities of the ibuprofen and paracetamol drug ligands and its

complexes were carried out against the Escherichia Coli (Gram -ve), Bacillus subtilis (Gram +ve) and

antifungal (tricoderma and penicillium activities). The antimicrobial activity estimated based on the size

of inhibition zone around dishes. The ibuprofen complexes were found to have high activity against

Bacillus subtilis and penicillium, whereas the Cu(II) complex was more active than the Fe(III) , Mn(II)

and Co(III)complexes against tricoderma. The paracetamol complexes were found to have high activity

against Bacillus subtilis and penicillium, whereas the Fe(III) complex was more active than the Mn(II),

Co(II) and Cr(III) complexes against tricoderma.

3-7- Suggested structures of ibuprofen and paracetamol complexes

The structures of both complexes of ipuprofen and paracetamol with Cr(III), Fe(III), Mn(II) and

Co(II) ions (Fig. 2 and 3) have been confirmed from the elemental analyses, IR, molar conductance, UV-

Vis, mass and thermal analysis data.

4. CONCLUSION

Ibuprofen and paracetamol are a very interesting ligand from point of view of its applications. It

could form several complexes with metal (II) ions. In this paper, the synthesis and properties of these

types of compounds was investigated. The complexes with the empirical formulas: Mn2(Ibu)4(H2O)2,

Co2(Ibu)4(H2O)2, Fe2(Ibu)4(H2O)2, Cu(Ibu)2(H2O)2, Mn(Par)2, Co(Par)2, Fe(Par)2(OH)(H2O), and

Cr(Par)2(OH)(H2O) were prepared as a solid compounds. The structures of the complexes of Ibu and Par

with Mn(II), Co(II), Fe(III) and Cu(II) have been confirmed from the elemental analysis, FT-IR

spectroscopy and thermal analysis. Thus, from the FTIR spectrum, it is concluded that both Ibu and Par

behave as a monobasic bidentate ligand co-ordinated to the metal ion. The co-ordination water, evidenced

by FT-IR spectroscopy, was confirmed and determined by thermal analysis, in the TG curve. The thermal

investigation (studied by TG/DTG techniques) shows that obtained complex decomposes progressively,

and the first step of thermolysis is dehydration. The final product of the thermal decomposition is metal

oxides, which through its percentage confirms the empirical formulae of the new complexes prepared.

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The authors declare no conflict of interest

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