The Malaysian Journal of Analytical Sciences Vol 17 No 2 (2013): 214 - 223

 

 

 

Sintesis dan Penentuan Struktur Kompleks Di-tert-butilstanum (IV) Ditiokarbamat

 

(Synthesis and Structure Determination of Di-tert-butyltin (IV) Dithiocarbamate)

 

Amirah Faizah Abdul Muthalib, Ibrahim Baba*, Yang Farina Abdul Aziz, Mohd Wahid Samsudin

Pusat Pengajian Sains Kimia dan Teknologi Makanan, Fakulti Sains dan Teknologi,

Universiti Kebangsaan Malaysia, 43600 UKM Bangi, SelangorD.E.

 

*Corresponding author:aibi@ukm.my

 

 

Abstrak

Kompleks diorganostanum(IV) ditiokarbamat baru telah disintesis daripada di-tert-butilstanum(IV) diklorida dengan kehadiran bersama N-dialkilamina dan karbon disulfida. Analisis unsur dan gravimetri menunjukkan formula umum bagi kompleks ini ialah (t-C₄H₉)₂Sn[S₂CNR₁R₂]₂ (R₁ = CH₃, C₂H₅, C₇H₇ dan R₂ = C₂H₅, C₆H₁₁, iC₃H₇, CH₃, C₂H₅, C₄H₉, C₇H₇). Struktur kesemua kompleks ditentukan dengan menggunakan spektroskopi inframerah, ultralembayung, ¹H, ¹³C dan ¹¹⁹Sn RMN dan kristalografi sinar-X. Analisis termogravimetri bagi kompleks yang telah diperoleh juga turut dibincangkan. Spektrum inframerah semua kompleks ini menunjukkan tiga jalur v(CN), n(CS) dan v(Sn-S) yang wujud masing-masing pada julat 1447-1496, 947-988 dan 352-370 cm^-1. Spektroskopi ¹³C RMN menunjukkan anjakan kimia untuk δ(N¹³CS₂) berada pada julat 199.1–201.8 ppm. Struktur hablur tunggal sinar-X bagi kompleks (t-C₄H₉)₂Sn[S₂CN(CH₃)(iC₃H₇)]₂ menunjukkan atom pusat stanum berkoordinat enam dan hablur mempunyai sistem monoklinik dengan kumpulan ruang P2/n, dengan a = 11.2934(11) Å, b = 7.0175(7) Å, c = 15.6894(15) Å; β = 95.016(1)^o. Manakala kompleks (N-benzil-N-etilditiokarbamato)klorido di-tert-butilstanum(IV) dan (N,N-dibenzilditiokarbamato)klorido-di-(tert-butil)stanum(IV) hanya mempunyai satu ligan ditiokarbamat dan satu atom klorin dengan membentuk struktur lima koordinatan. Hablur (N-benzil-N-etilditiokarbamato)klorido di-tert-butilstanum(IV) bersistem triklinik di mana a = 8.6140 (2) Å, b = 10.9604 (3) Å, c = 11.4765 (3) Å; α = 91.858 (2)˚, β = 96.193 (2)˚, γ = 96.011 (2)˚, dengan kumpulan ruang P1. Manakala (N,N-dibenzilditiokarbamato)klorido-di-(tert-butil)stanum(IV) bersistem monoklinik di mana a = 9.0600 (2) Å, b = 10.9238 (2) Å, c = 12.7845 (3) Å; β = 102.759 (2)˚ serta berkumpulan ruang P2_i.

 

Kata kunci: di-tert-butilstanum(IV), ditiokarbamat

 

Abstract

New diorganotin(IV) dithiocarbamate complexes have been synthesized from di-tert-butyltin(IV) dichloride, N-dialkylamine and carbon disulphide. Elemental and gravimetric analysis confirmed the general formula of these complexes as (t-C₄H₉)₂Sn[S₂CNR₁R₂]₂ (R₁ = CH₃, C₂H₅, C₇H₇ dan R₂ = C₂H₅, C₆H₁₁, iC₃H₇, CH₃, C₂H₅, C₄H₉, C₇H₇). The structures of these complexes have been elucidated on the basis of infrared, ultraviolet, ¹H, ¹³C & ¹¹⁹Sn NMR spectroscopy and X-ray crystallography. The infrared spectra of these complexes showed three main peaks for v(CN), n(CS) and v(Sn-S) bands that appeared in the region of 1447-1496, 947-988 and 352-370 cm^-1, respectively. The ¹³C NMR spectrum showed the chemical shift for δ(N¹³CS₂) in the range of 199.1–201.8 ppm. X-ray single crystal structure (C₄H₉)₂Sn[S₂CN(CH₃)(iC₃H₇)]₂ demonstrated a six-coordination geometry around the tin atom adopting a monoclinic system with a space group of P2/n with a = 11.2934(11) Å, b = 7.0175(7) Å, c = 15.6894(15) Å; β = 95.016(1)^o. The (N-benzyl-N-ethyldithiocarbamato)chlorido di-tert-butyltin(IV) and (N,N-dibenzyldithiocarbamato)chlorido-di-(tert-butyl)tin(IV) formed a different geometry with one dithiocarbamate ligand and one chlorine atom attached to the tin centre to form a five-coordinate structure. Crystal of (N-benzyl-N-ethyldithiocarbamato)chlorido di-tert-butyltin(IV) adopts a triclinic system with  space group of P1 and cell parameter of a = 8.6140 (2) Å, b = 10.9604 (3) Å, c = 11.4765 (3) Å; α = 91.858 (2)˚, β = 96.193 (2)˚, γ = 96.011 (2)˚, while (N,N-dibenzyldithiocarbamato)chlorido-di-(tert-butyl)tin(IV) adopts a monoclinic system with space group  of P2_i with cell parameter a = 9.0600 (2) Å, b = 10.9238 (2) Å, c = 12.7845 (3) Å; β = 102.759 (2)˚.

 

Keywords: di-tert-butyltin(IV), dithiocarbamate

 

References

1.        Debus, H. (1850). Uber die Verbindungen der sulfocarbamisaur. Agnew Chemistry (Liebigs), 73: 26.

2.        Thorn, G.D. and Ludwig, R.A. 1962. The Dithiocarbamates and Related Compounds. Amsterdam-New York: Elsevier Publishing Company.

3.        Kim, K., Ibers, A.J., Jung, O.S. and Sohn, S.Y. (1987). Structure of Di(tert-butyl)bis(N,N-dimethyldithiocarbamato)tin(IV). Acta Crystallographica,  C43: 2317-2319.

4.        Frank, N., Christmann, A. and Frei, E. (1995). Comparative studies on the pharmacokinetics of hydrophilic prolinedithiocarbamate, sarcosinedithiocarbamate and the less hydrophilic diethyldithiocarbamate. Toxicology, 95: 113-122.

5.        Gandhi, N., Jain, R. and Kaushik, N. K. (1996). Thermal studies on germanium(IV) compounds of N-alkylcyclohexyldithiocarbamates. Thermochimica Acta, 282/283: 501-508.

6.        Gessner, T. and Jakubowski, M. (1972). Diethyldithiocarbamic acid methylester *1: A metabolite of disulfiram. Biochemical Pharmacology, 21(2): 219-230.

7.        Radha, K., Aravamudan, G., Rajalakshmi, A., Rout, G.C. and Seshasayee M. (1986). Synthesis and properties of tris(bis(2-hydroxyethyl)-dithiocarbamato)halotellurium(II) (‘halo’=SCN^-, Br^-, I^-) and the crystal structure of the thiosyanato-S complex, [Te₂{(HOCH₂CH₂)₂NCS₂}₃SCN]. Australian Journal Chemical Society, 39: 847-854.

8.        Okamoto, K., Kirchoff, J.R., Ho, D.M. and Deutsch, E. (1993). Preparation, characterization and electrochemical properties of technetium(II) complexes with 1, 2-bis(diethylphosphino) ethane (DEPE) and dithiocarbamate ligands. Single crystal analysis of [Tec{(CH₃)₂NCS₂}(DEPE)₂(PF₆)]. Polyhedron 12(12): 1559-1568.

9.        Shahzadi, S., Ali, S. and Fettouhi, M. (2006). Dimethylbis(4-methylpiperidine-1-dithiocarboxylato-²S,S')tin(IV). Acta Crystallographica E62: 1178.

10.    Thirumaran, S., Venkatachalam, V., Manohar, A., Ramalingam, K., Bocelli, G. and Cantoni, A. (1998). Synthesis and characterization of bis(N-Methyl-N-ethanoldithiocarbamato)M(II)(M = Zn, Cd, Hg) and bis(N,N-(iminodiethylene)bisphthalimidedithiocarbamato)M(II) (M = Zn, Cd, Hg) complexes. Single crystal X-ray structure of bis(di(2-hydroxyethyl)dithiocarbamato)zinc(II). Journal of Coordination Chemistry 44: 281-288.

11.    Bruker. (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

12.    Sheldrick, G. M. (2008). Software reference manual, Siemens Analytical X-ray System, Madison, WI, USA.

13.    Barbour, L. J. (2001). E-Seed – A software tool for supramolecular crystallography. Journal Supramolecular Chemistry, 1: 189–191.

14.    Jung, O.S. and Sohn, S.Y. (1988). Coordination Chemistry of Organotin(IV) Dithiocarbamate Complexes. Bulletin of the Korean Chemical Society, 9: 356-368.

15.    Chauhan, H.P.S. and Shaik, N.M. (2005). Synthetic, spectral, thermal and antimicrobial studies on some mixed 1,3-dithio-2-stannacyclopentane derivatives with dialkyldithiocarbamates. Journal of Inorganic Biochemistry, 99: 538–545.

16.    Singh, R. and Kaushik, N.K. (2008). Spectral and thermal studies with anti-fungal aspects of some organotin(IV) complexes with nitrogen and sulphur donor ligands derived from 2-phenylethylamine. Spectrochimica Acta Part A, 71: 669–675.

17.    Jian, F. F., Wang, Z. X., Bai, Z. P., You, X. Z., Fun, H. K., Chinnakali, K. (1999). Structure of bis(dipropyldithiocarbamate) cadmium(II). Journal of Chemical Crystallography, 29: 227 – 231.

18.    Sharma, C. P., Kumar, N., Khandpal, M. C., Chandra, S. and Bhide, V. G. (1981). Studies on the preparation and characterization of bis-dithiocarbamato derivatives of di-n-butyl- and di-n-hexyl Sn(IV). Journal Inorganic Nuclear Chemistry, 43: 923-930.

19.    Casas, J. S., Sanchez, A., Bravo, J., Fontan, S., Castellano, E. E., Jones, M., (1989). Cadmium(II) coordination chemistry related to chelate therapy. Inorganica Chemica Acta, 158: 119 – 126.

20.    Cea-Olivares, R., Toscano, R.A., Silvestru, C., Garcia-García, P., López-Cardoso, M., Blass-Amador, G. and Nöth, H. (1995). Synthesis and structural characterization of phenoxarsin-10-yl dithiocarbamates, O(C₆H₄)₂AsS₂CN(CH₂CH₂)₂, a compound containing an asymmetric mononuclear biconnective 1,1-dithiolato ligand. Journal of Organometallic Chemistry, 493: 61-67.

21.    Khan, S., Nami, S.A.A., Siddiqi, K.S. (2008). Mononuclear indolyldithiocarbamates of SnCl₄ and R₂SnCl₂: Spectroscopic, thermal characterizations and cytotoxicity assays in vitro. Journal of Organometallic Chemistry 693: 1049–1057.

22.    Shaheen, F., Badshah, A., Gielen, M., Dusek, M., Fejfarova, K., de Vos, D. and Mirza, B. (2007). Synthesis, characterization, antibacterial and cytotoxic activity of new palladium(II) complexes with dithiocarbamate ligands: X-ray structure of bis(dibenzyl-1-S:S0-dithiocarbamato)Pd(II). Journal of Organometallic Chemistry, 692: 3019–3026.

23.    Husaina, A., Nami, S.A.A. and Siddiqia, K.S. 2009. Interaction of organotin with piperazine derived self-assembled cylindrical bisdithiocarbamates: Spectral and thermal investigations. Spectrochimica Acta Part A 73: 89–95.

24.    Van Gaal, H. L. M., Diesveld, J. W., Pijpers, F. W and Vander Linden, J. G. M. (1979). ¹³C NMR spectra of dithiocarbamates. Chemical shift, carbon-nitrogen stretching vibration frequencies, and p bonding in the NCS₂ fragment. Inorganic Chemistry, 18(11): 3251-3260.

25.    Nomura, R., Takabe, A. and Matsuda, H. (1987). Facile synthesis of antimony dithiocarbamate complexes. Polyhedron, 6(3): 411-416.

26.    Agustin, D. and Ehses, M. (2009). ¹¹⁹Sn NMR spectroscopic and structural properties of transition metal complexes with terminal stannylene ligands. Comptes Rendus Chimie, 12: 1189-1227.

27.    Schiemenz, B., Huttner, G., Zsolnai, L., Kircher, P. and Diercks, T. (2006). Two Extremes in Tin Chemistry: A Non-bonding Sn–Sn Distance of 285 pm and a ¹¹⁹Sn-NMR Shift δ = 3301 in Organometallic derivatives of Sn(0). European Journal of Inorganic Chemistry 128(2): 187-191.

28.    Holecek, J., Nadvornik, M., Handlir, K., Lycka, A. (1986). ¹³C and ¹¹⁹Sn NMR spectra of Di-n-butyltin(IV) compounds. Journal of Organometallic Chemistry, 315: 299-308.

29.    Zhang, R., Sun, J. and Ma, C. 2005. Structural chemistry of mononuclear, tetranuclear and hexanuclear organotin(IV) carboxylates from the reaction of di-n-butyltin oxide or diphenyltin oxide with rhodanine-N-acetic acid. Journal of Organometallic Chemistry, 690: 4366-4372.

30.    Muthalib, F.A., Baba, I., Samsudin, W.M. and Ng, W.S. (2010). Ditert-butylbis(N-isopropyl-N-methyldithiocarbamato-k²S,S’)tin(IV). Acta Crystallographica, E66:m356.

31.    Muthalib, A. F. A., Baba, I., Tahir, M. I. M., Ng, S. W. and Tiekink, E. R. T. (2011a). (N-Benzyl-N-ethyldithiocarbamato)-di-tert-butylchloridotin(IV). Acta Crystallographica, E67: 372-373.

32.    Muthalib, A. F. A., Baba, I., Tahir, M. I. M., Ng, S. W. and Tiekink, E. R. T. (2011b). Di-tert-butylchlorido(N,N-dibenzyldithiocarbamato)tin(IV). Acta Crystallographica, E67: 386.