Sains Malaysiana 31: 101-108 (2002)                                                                           Sains Fizis dan Gunaan /

                                                                                                                                                Physical and Applied Sciences

 

Synthesis and Characterizations of Ethylbutyldithiocarbamate Compounds: Crystal Structure of Bismuth(III)

Ethylbutyldithiocarbamate

 

 

Karimah Kassim, Ibrahim Baba, Yang Farina,

Abdul Hamid Othman & H.K. Fun

Pusat Pengajian Sains Kimia dan Teknologi Makanan

Fakulti Sains dan Teknologi

Universiti Kebangsaan Malaysia

43600 UKM Bangi, Selangor Malaysia

 

 

 

 ABSTRACT

 

A new series of ethylbutyldithiocarbamate compounds have been synthesized. The compounds made of Zn(II), Cu(II), Ni(II), Pb(II), Sb(III) and Bi(III) were prepared by reacting the respective metal salts with ethylbutylamine and carbon disulphide using "in situ" method. Results of elemental analysis showed that the isolated compounds have the general formula, M[S2CNR1RZ2]n (n = 2; M = Zn(II), Cu(II), Ni(II), Pb(II), and n = 3; M = Sb(III) and Bi(III)). Infrared spectra of the compounds showed the thioureido v(C-N) bands in the regions 1468 – 1497 cm-1.  The (C-S) bands appeared in the region 956 – 997 cm-1  while the v(M-S) bands appeared in the region 300 – 400 cm-1.  The 1H NMR signals indicated ethyl- and butyl- in the region 0.40 – 3.85 ppm.  The 13C NMR spectra of zinc(II) and lead(II) showed a resonance in the region 202.0 ppm, which attributed to the carbon atom of NCS2 group.  Tris(N-ethyl-N-butyldithiocarbamato-S) bismuth(III) is pentagonal pyramid distorted with triclinic system with P1, a = 10.5120(1)Å, b = 10.5128(1)Å, b = 10.5128(1)Å, c = 14.5755(1)Å, α = 99.927(1)o, γ = 103.3383(1) and Z = 2.

 

 

ABSTRAK

 

Kompleks etilbutilditiokarbamat telah berjaya disintesis. Zinke(II), nikel(II), kuprum(II), plumbum(II), stibium(III) dan bismuth(III) etilbutilditiokarbamat disintesis dengan tindak balas secara stoikiometri sebatian garam logam di atas dengan etibutilamina dan karbon disulfida menggunakan kaedah in situ dalam larutan etano1. Analisis unsur dan gravimetri menunjukkan setiap kompleks ditiokarbamat mempunyai formula yang dijangkakan, iaitu M[S2CNR1R2]n (di mana n = 2; M = zink, kuprum, nikel, plumbum dan n = 3; M = stibium, bismuth). Analisis spektroskopi inframerah kompleks etilbutilditiokarbamat menunjukkan serapan pada julat 1468 - 1497 cm-1 hasil daripada regangan tioureida v(C-N) dan serapan pada julat 956 - 997 cm-1 adalah hasil daripada regangan ikatan v(C=S). Kompleks ini memberikan julat serapan pada 300 - 400 cm-1 hasil daripada regangan v(M-S). Analisis 1H RMN bagi kompleks etilbutilditiokarbamat menunjukkan resonans proton bagi kumpulan etil- dan butil- dalam julat 0.40 - 3.85 ppm. Analisis 13C RMN bagi sebatian zink(II) dan plumbum(II) menunjukkan puncak N13CS2 berada dalam kawasan anjakan kimia 202.0 ppm. Kompleks Tris(N-etil-N­butilditiokarbamato-S) bismuth(III) berstruktur piramid pentagon terherot dengan sistem triklinik dengan P(1, a = 10.5120(1)Å., b = 10.5128(1)Å., c = 1'4.5755(1)Å., α = 99.713(1)o, β = 99.927(1) 0, γ = 103.3383(1)° dan Z = 2.

 

 

 

RUJUKAN/REFERENCES

 

Baba, I., Sukeria, I., Yang Farina, A. Hamid, 0., Ibrahim, A.R., Fun, H.K. & Ng, S.W. 2001. Tris(N-cyclohexyl-N-methlydithiocarbamato-S)-antimony(III). Acta Cryst. Sec. E. E57: 39-40.

Baba, I.,  Yang Farina,   Karimah  K., A. Hamid,   Othman.,    Ibrahim, A. R., Fun,   H.  K. & Ng, S. W. 2001. Bis (-N-ethlydithiocarbamato-S:S')bis[N-butyl-N­ethyldithiocarbamato)zinc(II). Acta Cryst. Sec. E. E57: 55-56.

Chatt, 1., Duncanson, L., A. & Venanzi, L., M. 1956. Electronic Structures of Dithiocarbamates and Xanthes. Nature 177: 1042-1043.

Coucouvanis, D.& Fackler, J.P. Jr. 1976. Square-planar Sulphur Complexes. Prog. Inorg. Chem. 21: 55.

Criado, J.J., Fernandez, 1. & Macias, B. 1990. Novel Chelates of Pd(II) Dithiocarbamates, Spectroscopic Studies and Thermal Behaviour. Inorg. Chim. Acta. 174: 67-75.

Jian, F.E, Wang, Z. X., Fun, H. K., Bai, Z. P. & You, X. Z. Acta Cryst. 1999, C55, 174 - 176.

Johnson, C. K. 1976. ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.

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

Sharma, C.P., Kumar, N., Khandpal, M.C., Chandra, S., & Bhide, V.G. 1981. Studies on the Preparation and Characterization of bis-dithiocarbamato derivatives of di­n-butyl- and di-n-hexyl Sn(IV). J. Inorg. Nucl. Chem. 43: 923 - 930.

Shieldrick, G. M. 1997. SHELX97 and SHELX97. University of Gottingen, Germany. Siemens. 1996. SAINTS and SMART. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Siemens, 1996. SAINTS and SMART.  Siemens analytical X-ray Instruments Inc., Madiosn, Wisconsin, USA.

Venkatachalam, V., Manohar, A., Thirumaran, S., Ramalingam, K., Bocelli, F., Cantoni, A. 1998. Synthesis, spectral and single crystal X-ray structural studies on (2,2’-bipryridyl) bis(dimenthyldithiocarbamato) zin(II) and (1,10-phenthroline) bis(dimethyldithiocarbamato)zinc(II). J. Chem. Cryst. 28: 861-866.

Venkatachalam, V., Manohar, A., Thirumaran, S., Ramalinganm, K., Bocelli, F., Cantoni, A. 1997. Structural and elestronic effects of alkyl substituents on the main group dithiocarbamato complexes: crystal and molecular structure of tris(N, N’-iminodiethanoldithiocarbamato metal(III) complexes (M=As, Sb and Bi) voltammetric studies on substituted dithiocarbamato. Polyhedron 16: 1211-1221.

 

 

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