Sains MaJaysiana 33(2): 35-43 (2004)                                                                                          Sains Fizis dan Gunaan /

Physical and Applied Sciences

Sintesis dan Pencirian Kompleks Organostanum(Iv) sek-Butilpropilditiokarbamat: Struktur Hablur Bis(N, N-­sek –butilpropilditiokarbamato) dimetilstanum(IV)

(Synthesis and Characterization of Organotin(IV) Sec-butylpropyldithiocarbamate

 Complexes: Structure of Bis(N, N-Sec-butylpropyl-dithiocarbamate crystals)

Normah Awang, Ibrahim Baba & Yang Farina Abdul Aziz

Pusat Pengajian Sains Kimia & Teknologi Makanan

Fakulti Sains dan Teknologi

Universiti Kebangsaan Malaysia

43600 UKM. Bangi, Selangor D.E., Malaysia

ABSTRAK

Kompleks baru organostanum(IV) sek-butilpropilditiokarbamat telah berjaya disediakan melalui tindak balas di antara N-sek-butil-N-propilamina, karbon disulfida dan sebatian dimetilstanum(lv), dibutilstanum(IV) dan trifenilstanum(IV) klorida menggunakan kaedah in-situ. Kesemua kompleks telah dicirikan menggunakan analisis unsur, analisis gravimetri, spektroskopi inframerah dan spektroskopi resonans magnet nukleus ¹H dan ¹³C. Analisis unsur (CHNS) dan gravimetri menunjukkan sebatian yang disintesis bersetuju dengan formula yang dicadangkan, iaitu R₂Sn[S₂CN(s-C₄H₉)(C₃H₇)]₂ dan R'₃Sn[S₂CN(s-C₄H₉)(C₃H₇] (R = CH₃ atau C₄H₉; R' = C₆H₅). Kehadiran jalur serapan v(C ---- N) dan v(C ---- S) pada spektrum inframerah menunjukkan kehadiran ligan ditiokarbamat dalam sebatian yang disediakan. Spektrum RMN ^I3C bagi ketiga-tiga kompleks menunjukkan resonan N¹³CS₂ terletak pada julat 196.22- 200.61 ppm. Kompleks dimetilstanum(1V) sek­bufilpropilditiokarbamat telah berjaya dihablurkan menggunakan pelarut kloroform. Kajian kristalograji sinar-X menunjukkan hablur Me₂Sn[s-­C₄H₉)(C₅H₇)]₂ bersistem monoklinik dengan kumpulan ruang P2₁/n, a = 14.358(2), b = 10.6956(18), c = 17.323(3) Å; α = 90°, β= 99.765(4)°, γ = 90°. Kompleks membentuk geometri enam koordinat dengan atom pusat stanum yang berikat dengan dua kumpulan metil pada kedudukan sis dan mengkelat secara bidentat dengan ligan sek-butil propilditiokarbamat.

ABSTRACT

New organotin(IV) sec-butylpropyldithiocarbamate complexes have been suc­cessfully synthesized by the reaction between N-sec-butyl-N-propylamine, carbon disulfide and organotin(IV) chloride (dimethyltin(IV), dibutyltin(IV) and triphenyltin(lV) chloride) using in-situ method. All the complexes have been characterized using elemental analysis, gravimetric analysis, infrared and NMR (¹H and ^I3C) spectroscopy. Elemental and gravimetric analyses showed that the complexes agree with the suggested formulae, R₂Sn[S₂CN( s­C₄H₉)(C₃H₇)]₂ dan R‘₃Sn[S₂CN(s-C₄H₉)(C₃H₇)] (R = CH₃ or R = C₄H₉; R' = C₆H₅ The presence of the v(C = N) and v(C = S) bands in the infrared spectra confirmed the presence of dithiocarbamate ligand in that complex. The ¹³C NMR spectra for all the complexes showed a resonance in the region 196.22 - 200.62 ppm, which is attributed to the carbon atom of NCS₂ group. The dimethyltin(lV) sec-butylpropyldithiocarbamate, Me₂Sn(SBPDtc)₂ was recrystallized from CHCl₃ and the structure had been determined using X-ray crystallography analysis. The structure of Me₂Sn[s-C₄H₉)(C₃H₇)]₂ is found to be in the monoclinic system with space group P2₁/n, a = 14.358(2), b = 10.6956(18), c = 17.323(3) Å; α = 90°, β = 99.765(4)°, γ = 90°. The complex is six-coordinated with the tin atom bonded by two dimethyl groups in cis positions and two chelating sec-butylpropyldithiocarbamates in bidentate mode.

RUJUKAN/REFERENCES

Bonati, F. & Ugo, R. 1967. Organotin(IV) N,N-disubstituted dithiocarbamates. J. Organometallic Chem. 10: 257-268.

Criado, J.J., Lopez-Arias, J.A. & Macias, B. 1992. Au(III) complexes of tris­dithiocarbamate derivatives of a-amino acids: spectroscopic studies, thermal behaviour and antibacterial activity. Inorg. Chimica Acta 193: 229-235.

Hall, V.I. & Tiekink, RT. 1998. The importance of varying the Lewis acidity of R₂Sn in determining the molecular structure of R₂Sn(1, 1-dithiolate) compounds: The crystal and molecular structures of three divinyltin N,N-dialkyldithiocarbamates. Main Group Met. Chem. 21 (5): 245-254.

Hibbert, T.G., Mahon, M.F. & Molloy, K.C. 1999. Organotin dithiocarbamate chlo­rides: X-Ray structures of n-Bu₂Sn(S₂CNEt₂)₂Cl₂ and n-BuSn(S₂CNEt₂)₂Cl. Main Group Met. Chem. 22(4): 235-241.

Manoussakis, G.E. & Tsipis, C.A. 1973. Preparation and study of some arsenic and antimony trisdithiocarbamates. J. Inorg. Nucl. Chem. 35: 743-750.

Sharma, R.K. & Sharma C.P. 1987. Synthesis and spectroscopic investigations on bis­dithiocarbamato complexes of i-p-tert-butylphenyltin(IV). J. Indian Chem. Soc. LXIV:205-208.

Sharma, J., Singh, Y, Bohra. R & Rai, A.K. 1996. Synthesis and spectral studies of diorganotin heterocyclic dithiocarbamate complexes: The crystal structure of (CH₃),Sn[S₂CNCH₂CH₂CH₂CH₂CH₂]₂. Polyhedron 7: 1097-1102.

Sharma, 1., Singh, Y.P. & Rai, A.K. 2000. Synthesis, characterization and structural eludication of monoorgano di(chloro) tin(IV) complexes of heterocyclic dithiocarbamates. Main Group Met. Chem. 23(5): 317-320.

Thirumaran, S., Venkatachalam, V., Manohar, A., Ramalingan, K., Bocelli, G. & Cantoni, A. 1998. Synthesis and characterization of bis(N-methyl-N­ethanoldithiocarbamato) M(II) (M = Zn, Cd, Hg) complexes and bis(N,N­(iminodiethylene) bisphthalimidedithiocarbamato)M(II) (M = Zn, Cd, Hg) com­plexes. Single crystal X-ray structure of bis[di(2-hydroxyethyl)dithiocarbamato J. zinc(II). J. Coord. Chem. 44: 281-288.