Polyhedron Vol. 3, No. 6, pp. 68-688, 1984 Printed in Great Britain.

02175381/84 $3.00+.00 0 1984 Pergamon Press Ltd.

STRUCTURAL FEATURES OF SOME ORGANOTIN(IV) COMPLEXES OF SEMI- AND THIO-SEMICARBAZONESS

ANIL SAXENAf and J. P. TANDON* Department of Chemistry, University of Rajasthan, Jaipur 302004, India

(Received 17 August 1983; accepted 23 September 1983)

Abstract-Some five- and six-coordinated di and tri-n-butyl tin(W) semi- and thio-semi carbazates have been synthesized. The characterization of these complexes, by IR, NMR (‘H, 13C, ‘19Sn), r19Sn Miissbauer and Mass spectroscopies along with X-ray diffraction, reveals that complexes of biionic ligands of the type Bu,Sn L” are five-coordinated having trigonal bipyramidal geometry. However, complexes of monoionic ligands of the type Bu,SnL; are six-coordinated in a distorted c&octahedral geometry and Bu,SnL’ are five-coordinated with a trigonal bipyramidal structure. X-ray structural studies on the compound Bu2Sn(0.C6H4.CH:N.N.CS.NH2), show that it crystallizes in a monoclinic lattice with a = 16.90 A, b = 9.71 A, c = 8.60 A, and /3 = 103”45’.

Semicarbazones and thiosemicarbazones are amongst the most important nitrogen- oxygen/sulphur donor ligands.’ Both of these ligands are capable of acting as neutral or charged ligand moieties. During the past few years, a plethora of references describing the transition metal complexes of these ligands have appeared in the literature.2*3 However, little is known about the complexing behaviour of non-transition elements with these ligands.4 Amongst the non-transition elements, tin occupies an important position as a number of modern physicochemical techniques can be applied for the detailed structural study of its compounds. It was, therefore considered of interest to react organotin oxides with semi- and thio- semicarbazones;

R-C=N-NH-!-NH

XH

R

2 = RC=N-N=C-NH,

R

(where X = 0 or S)

681

*Author to whom correspondence should be ad- dressed.

TPresent address: School of Chemistry and Molecular Sciences, University of Sussex, Brighton, BNl 9Q1, England.

IPresented at XXII Int. Conf. Coord. Chem., Hungary, 1982.

and carry out detailed systematic studies of the resulting compounds.

EXPERIMENTAL Chemicals and solvents used were dried and

purified by standard methods, and moisture was excluded from the glass apparatus using CaCl, drying tubes. The ligands were prepared by the literature method’ and all the manipulations were carried out under absolutely dry conditions. The complexes were prepared by a method similar to that reported in an earlier publication.6 The details are given in Table 1.

The complexes were analyzed by the literature methods and the molecular weights were deter- mined by the Gallenkamp ebulliometer or cryo- scopically in freezing benzene. ‘19Sn Mossbauer spectra were recorded with Bau9Sn03 source at 77 K and the isomer shift values are relative to SnO,. The X-ray powder diffractogram of the compound was obtained on a Phillips PM 9929/05 automatic diffractometer with Fe& target. The structure was solved by Ito’s method.’ The details of spectroscopic measurements are similar to those reported earlier.6

RESULTS AND DISCUSSION

Reaction of di-n-butyl and tri-n-butyl tin oxides with these ligands have been carried out in 1 : 1 and 1 : 2 molar ratios in refluxing benzene. These reac- tions proceed with the liberation of water, which is

682 A. SAXENA and J. P. TANDON

Table 1. Analyses and physical characteristics of organotin complexes

Compound Mol. wt. M p

Colour and State Analyses % Found (Calcd.) Found * ’ ( Calcd. ) ‘C (Yield % ) S% Sn % C% H%

Bu2Sn( C9H9N30S) A1

Bu2Sn(CsH7N30S) A2

Bu2WC12H9N30S) A3

Bu2WCsH8N3S)2 A4

Bu3WCsHsN3S) A5

Bu3WC9HloN3S) A6

B’J~S”(C~H~N~O~) A,

Bu2W CsH,N302) As

8~2Sn(C9Hl~N~O)2 A9

S”2WC8HsN30)2 Alo

Bu3Sn(C9H10N30) AU

Bug&( C8H8N30) A12

405

(426) 4%

(478) 565

(589)

(z8)

498

(482)

:z

402

(410)

572

(585)

57s

(557)

(Z,

440

(452)

81

87

91

185

192

Yellow solid

( 94) Dark yellow solid

( 92 ) Red semi -solid

(90) Orange semi -solid

(92)

Brown yellow Beti solid

( 88)

Yellow semi solid

( 861 Light green yellow solid

(92) Yellow semi -solid

(90)

Brown yellow-solid

( 94 )

6.52 (7.27)

7.05

c/. 51)

5.91 (6.72)

10.13 (lo. 86)

6.23 (6.88)

5.88 (6.65)

26.92 ( 27.03)

27.48 (27.98)

24.72 (25.02)

20.36 (20.18)

25.00 (25.45)

24.05 (24.73)

27.82 (28.05)

28.52 (29.00)

21.05 (20.33)

Cream yellow-solid 21.12

(90) (21.43)

Brown semi -solid 25.81

(90) (25.57)

Cream yellow semi -solid 26.05

(90 ) (26.38)

45.87 5.58 (46.37) (6.13)

46,95 6.32 (45.07) (5.86)

48.23 6.81 (50.42) (6.09)

47.12 6.06 (48.89) (5.77)

50.10 7.83 (51.61) (7.52)

53.21 7.05 (52.39) (7.69)

47.05 5.80 (48.11) (6.36)

47.82 6.52 (46.83) (6.09)

51.88 5.91 (53.35) (6.49)

50.05 6.63 (51.89) (6.12)

55.83 7.32 (54.19) (7.95)

51.59 7.05 (53.21) (7.76)

Note: These complexes were also analyzed for the nitrogen contents.

removed azeotropically with benzene.

COH Bu,SnO + NLxH + Bu,Sn(c?) + H,O

Bu,SnO + 2fiH -+ Bu,Snfi), + H,O

(Bu,Sn),O + ZNhXH+2Bu,Sn(NhX) + HzO.

(where X = 0 or S)

The above reactions were found to be quite facile and could be completed in 8-10 hr of refluxing. The resulting complexes are obtained in good yields in the form of yellow to dark red coloured solids, semi-solids and viscous oils. These monomeric, low melting solids are soluble in most of the common organic solvents and susceptible to moisture.

In the IR spectra of ligands, a broad band is observed in the region, 3300-2850ctn’ . This band attributable to vOH and/or vNH does not appear in the complexes and in its place two sharp bands are observed at N 3310 and 313Ocm-’ due to the symmetric and asymmetric modes of NH, group.8

A sharp and strong band at 1635 cm-’ in these complexes compared to one at N 1620 cm-’ in the ligands may be assigned to vC=N. The shifting of

this band to higher frequency is probably due to an increase in the C=N bond order due to the coordi- nation of nitrogen with the metal atom. The Sri--- stretching vibration gives two bands, one near 600 cm-’ due to the tram form and the other one around 510 cm-’ due to the gauche form. Several new bands in the complexes at N 550, 425 and 340 cm-’ are probably due to vSn.0, vSn+N and v Sn-S respectively.6

The proton magnetic resonance spectral data of these complexes have been recorded in Table 2. The protons of -OH and -SH groups of the ligands give signals at 6 12.10 and 9.81 ppm and which are absent in the metal complexes indicating the coor- dination of tin with oxygen as well as sulphur atoms. The protons of the NH, group appear at 6 5 ppm in Bu,SnL, whereas in the case of Bu,SnL these are observed at 6 3.5 ppm. The protons of the aldehyde or ketonic -C--R group show marked shifting due to the coordination of > C=N with the tin atom. The protons of the butyl groups appear in the range of 6 0.5-1.9 ppm.

l19Sn Miissbauer parameters for two of these complexes have been derived and are recorded in Table 3.

The isomer shift values indicate the presence of tin in the +4 oxidation state and the presence of quadruple splitting shows that the EFG around the tin nucleus is produced by the inequalities in the

Structural features of some organotin(IV)

Table 2. ‘H NMR data (6 ppm) of ligands and organotin semi- and thiosemicarbazates

683

Compound -OH -NH -HI -CsH4* a3 -NH2 Sn( C4H9)

H

OH.C6H4.CH:N.N<ChH2 11.46 9.81 6.93 8.22 2.72

n-Bu2Sn(0.C6H4.CH:N.N:C.0.NH2 H A8 - - 7.01 8.35 4.95 0.7-1.8

0H.C6H4.CH:N.i&.NH2 ll.40 10.02 6.86 8.20 2.65

n-Bu2Sn(0.C6H4.CH:N.N:C.S.NH2) H

A2 - - 6.92 8.34 4.90 0.6-1.65

0H.C6H4.C(CH3)cN.N/CbH2 12.10 9.81 7.11 1.62 2.32 -

n-Bu2Sn(0.C6H4.C(CH3):N.N.C.S.NH2 Al - - 7.02 2.6 5.05 0.7-1.75

n-Bu2Sn(0.C10H6.CH:N.N.C.S.NH2) A3 7.42 9.35 4.85 0.75-1.70

n-Bl13Sn(0.C6 H5.CH:N.N.CD.NH2) A 12 - - 7. 51 9.46 3.45 0.7-2.1

n-EQ3Sn( C6H5.CH:N.N.C.S.NH2) A5 7.63 9.40 3.55 0.58-2.0

* Center of multiplet .

tin-ligand 0 bonds.g These compounds give a p are typical of Schiff base metal complexes. The value of 2.2 which indicates a coordination number fragmentation pattern for the former compound is greater than four. The monomeric six-coordinate given in Fig. 1 while for the latter, it has been structures seem to be most probable for these reported by us. l3 The 13C NMR spectral data of a compounds, as the isomeric shift and quadrupole few representative complexes relative to TMS have splitting values are well within the range been recorded in Table 4. The large change in 13C (1.63-2.56) prescribed for octahedral geometries chemical shifts in the spectra of the complexes with c&R groups. lo The point charge calculations compared to the ligands clearly shows the coordin- predict a A Eq value of 2 n-m-’ for the c&isomer ation of the azomethine nitrogen to the metal and 4mms’ for the tram isomer with no dis- atom. Compounds A,, A, and A, show ‘J values of tortion. A slightly higher value of AEq may be 607,565.2 and 598.2 Hz respectively and these are accounted for by considering a slight distortion characteristic of 5-coordinate tin. James et aLI4 from the ideal symmetry. ” The isomer shift values have reported a value of 586 Hz for dibutyl tin bis are also somewhat lower than trans analogues due (p-ethoxy-benzoate), while a ‘J (11gSn-13C) value to a decrease in the 5 s-character of the Sri--- cr equal to 614 Hz has been reported by Smith et al.” bonds. Naik et al.” have reported 6 values (0.92 for compounds having five coordination around and 1.45 mms-‘) for cis- and tram octahedral tin. The observation of two v(SnC,) bands in the Bu,Sn complexes. IR spectra rules out a strictly linear array.

The mass spectra of Bu,Sn(OC,H,.C(CH,): NNCSNH2) and Bu2Sn(OC,H,CH.NNCSNH2)

The compounds, BuSn(OC,H,.CH : NNCO- NH,), Bu3Sn(C,H5.CH : NNCONH,) and Bu,Sn (OC,H4.C(CH3 : NNCONH,) give sharp sig- nals in the “‘Sn spectra at d-189.1, d-104 and a-142.4 ppm respectively and these are in accord- ance with the proposed five coordinated structures. Smith et al. I6 have reported a value of 6 - 149.2 ppm for five coordinated Ph,SnONPhCOPh while a value of 6 -92 ppm has been reported by Otera” for Me,SnCl (Oxin).

Table 3. ‘19Sn Miissbauer data of organotin semi- carbazates

I.S. Q.S. mms-’ mms-’

1.08 2.36 0.98 2.23 X-Ray powder diffraction studies have been

carried out on Bu2Sn(OC6H4.CH : NNCSNH,) in

684 A. SAXENA and J. P. TANDON

r.

s

0 d 2

Structural features of some organotin(IV) 685

Tab

le

4 (C

od)

Ch

emic

al s

hif

ts i

n

6,

pp

m

stru

ctu

re

1

2

3

4

5

6

7

8

9

a B

Y

6

2

3

1

4 0

/O

H

6yhN

s”

- n

=C

N

H2

155.6

7 1

15.3

0 1

28.9

1 ll

9.0

3

126.5

8

l16.9

4

176.0

3

12.6

1

178.7

1

5

9 ao

y 6

C4H

9 ..

, /C

-C-C

-C

162.2

9 l

14.8

7

130.1

0 119.8

9

127.8

5

119.1

2

164.7

9

18.3

1

161.9

2 2

1.5

6

25.3

3

24.1

0

11.5

5

For

Al

f ( l1

9%

-13C

) =

565.2

Hz

“J (

119Sn-1

3C

) =

30.9

Hz

3

119

J (

Sn-1

3C

) =

84.3

H

z

Structural features of some organotin(IV) 687

I

‘+ -Bu ) @j-i l+

-NH%

I

-N-N=C--NH,

CHs CH,

Am/e440 Mt B m/e 383

I

=N-N=C-NH1

CH, CHs

D m/e 252

-sn+

C m/e 326

-cH3 * -HCN CHO 63

I t

9

E m/e 133 F m/e 118 C m/e 91

Fig. 1. Mass fragmentation of Bu,Sn(O.C&N$)

Table 5. X-Ray powder diffraction data for n-Bu2Sn(C,H,N30S) [A,]

“* *obsd. No.

d calcd.

hkl Sl. NO.

d obsd.

d calcd.

hkl

1. 16.63 16.90

2. 9.71 9.71

3. 8.71 a. 60

4. 0.42 8.45

5. 7.72 7.65

6. 6.39 6.39

7. 6.06 6.02

8. 5.62 5.63

9. 4.91 4.87

10. 4.72 4.71

11. 4.24 4.23

loo

010

007

200

101

210

201

300

310

301

311

21 3.07 3.07 0.31

22 3.02 3.02 230

23 2.89 2.91 511

24 2.85 2.86 003

25 2.81 2.81 600

26 2.77 2.75 013

27 2.74 2.73 113

28 2.68 2.70 610

29 2.54 2.55 611

30 2.38 2.38 700

31 2.34 2.34 no

12. 3.96 3.93 012 32 2.30 2.31 141

13. 3.85 3.83 112 33 2.25 2.26 711

14. 3.75 3.79 401 34 2.15 2.15 004

15. 3.69 3.67 320 35 2.u 2.ll 800

16. 3.50 3.53 411 36 2.06 2.06 810

17. 3.45 3.41 302 37 2.04 2.05 801

18. 3.37 3.38 500 38 1.94 1.94 050

19. 3.23 3.23 030 39 1.88 1.88 151

20. 3.14 3.18 510 40 1.84 1.80 911

POLY Vol. 3, No. 6-D

688 A. SAXENA and J. P. TANDON

order to determine the lattice dimensions of the 3. P. L. Maurya, B. V. Agarwala and A. K. Dey, J. compound. The indexed ‘d’ values are reported in Indian Chern. Sot. 1980, LVll, 275. Table 5. The compound crystallizes in a “Mono- 4. A. K. Saxena, J. K. Koacher and J. P. Tandon, J.

clinic’ type of lattice with the unit cell dimensions Inorg. Nucl. Chem. 1981, 43, 3091.

as under: 5. A. I. Vogel, A Text Book of Practical Organic Chemistry, p. 722. Longmans, London (1963).

a = 16.90 A fi = 103”.45’

b= 9.llA Z=6

c = 8.60 A.

The unit cell of the compound is made up of 6 molecules.

Acknowledgements-The authors are highly thankful to Prof. T. N. Mitchell (W. Germany) for very kindly recording the 13C and ‘19Sn NMR spectra. Thanks are also due to Dr. Prithviraj (B.A.R.C., Bombay) for kindly recording the X-ray diffractogram and Mijssbauer spec- tra. A. Saxena is grateful to the C.S.I.R., New Delhi for the award of P.D.F.

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Canad. J. Chem. 1960, 38, 712. 2. V. K. Arora, K. B. Pandeya and R. P. Singh, J.

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