Malaysian Journal of Analytical Aciences Vol 18 No 2 (2014): 251 – 259

 

 

 

SYNTHESIS, STRUCTURAL AND ANTIBACTERIAL STUDIES OF NEW DITHIOCARBAMATE COMPLEXES OF Sb(III) AND Bi(III)

 

(Sintesis, struktur dan kajian antibakteria kompleks baru ditiokarbamat Sb(III) dan Bi(III))

 

Nur Amirah Jamaluddin1, Ibrahim Baba1*,  Nazlina Ibrahim2

 

1School of Chemical Sciences and Food Technology,

2School of Biosciences and Biotechnology,

Faculty of Science and Technology,

Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia

 

*Corresponding author: aibi2005@gmail.com

 

 

Abstract

Six new dithiocarbamate complexes from three different amines, e.g. N-ethylethanol-, N-butylethyl- and N-benzylmethylamine  were successfully prepared using in situ method. All complexes were characterized by elemental analysis, IR, UV-Vis, 13C and 1H NMR. Elemental analysis data (C, H, N and S) showed an agreement with the general formula of MCl(S2CNR’R’’)2, (M = Sb(III), Bi(III); R’ = ethyl, butyl and benzyl; R” = ethanol, ethyl and methyl). The complexes had been characterized by infrared spectroscopy that showed a thioureide bands, n(CN) in the region of 1427 - 1490 cm-1 followed by n(CS) bands that can be seen in the region of 935 - 1060 cm-1 and ν(M-S) bands existed in the region of 350 - 392 cm-1. Maximum wavelength absorption for ultraviolet-visible spectroscopy for NCS group was at 254 nm which indicates π→π* transition. Data from 13C NMR showed a signal in the region of 198.39 – 199.44 ppm that corresponded to the NCS2 group. The crystal structure of bis(N,N’-butylethyldithiocarbamato)chlorido antimony(III), SbCl[S2CN(C4H9)(C2H5)]2 demonstrated a five-coordination geometry, triclinic system, space group P1 with a = 10.0141(8) Å, b = 10.1394(7) Å, c = 11.8665(9) Å, α = 67.960(2)°, β = 87.616(2)° and γ = 80.172(2)°. Minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) tests were done using five dithiocarbamate complexes which are BiCl[S2CN(C2H5)(C2H4OH)]2, SbCl[S2CN(C2H5)(C2H4OH)]2, BiCl[S2CN(C4H9)(C2H5)]2, SbCl[S2CN(C4H9)(C2H5)]2, BiCl[S2CN(C7H7)(CH3)]2 towards S. aureus, S. epidermidis, E. aerogenes and E. coli. It was found that all four complexes were active against S. aureus except SbCl[S2CN(C2H5)(C2H4OH)]2 while BiCl[S2CN(C7H7)(CH3)]2 and BiCl[S2CN(CH3)(C6H11)]2 complexes were active against S. epidermidis with MIC value of 5.0 mg/mL and 2.5 mg/mL respectively and MBC value of 5.0 mg/mL for both compounds. Only BiCl[S2CN(C2H5)(C2H4OH)]2 was active against E. aerogenes with MIC, 1.25 mg/mL and MBC, 10 mg/mL. All complexes were less active as antibacterial agent against E. coli strain.

 

Keywords: Dithiocarbamate, antimony(III), bismuth(III), antibacterial

 

Abstrak

Enam sebatian ditiokarbamat baru daripada tiga jenis amina yang berbeza, iaitu N-etilaminoetanol, N-butiletil, N-benzilmetil telah berjaya disediakan dengan menggunakan kaedah in situ. Kesemua sebatian telah dicirikan dengan analisis unsur, IR, UV-Vis, 13C dan 1H NMR. Data analisis unsur (C, H, N dan S) bagi kesemua sebatian menepati formula umum  MCl(S2CNR’R’’)2 (M = Sb(III), Bi(III); R’ = etil, butil dan benzil; R” = etanol, etil dan metil). Kompleks dicirikan menggunakan kaedah spektroskopi inframerah menunjukkan jalur tioreida, n(CN) berada dalam julat 1427 - 1490 cm-1 diikuti jalur n(CS) yang diperhatikan dalam julat 935 - 1060 cm-1 dan jalur logam sulfur, ν(M-S) berada dalam julat 350 - 392 cm-1. Serapan jarak gelombang maksimum untuk spektroskopi ultralembayung-nampak untuk kumpulan NCS ialah pada 254 nm yang menunjukkan peralihan π→π*. Data daripada 13C NMR menunjukkan isyarat dalam julat 198.39 – 199.44 ppm merujuk kepada kumpulan NCS2. Struktur hablur bis(N,N’-butiletilditiokarbamato)klorido stibium(III), SbCl[S2CN(C4H9)(C2H5)]2 menunjukkan geometri lima koordinatan, sistem triklinik, kumpulan ruang P1 dengan a = 10.0141(8) Å, b = 10.1394(7) Å, c = 11.8665(9) Å, α = 67.960(2)°, β = 87.616(2)° and γ = 80.172(2)°. Ujian kepekatan minimum perencatan (MIC) dan kepekatan minimum bakterisidal (MBC) telah dijalankan menggunakan lima sebatian ditiokarbamat, iaitu BiCl[S2CN(C2H5)(C2H4OH)]2, SbCl[S2CN(C2H5)(C2H4OH)]2, BiCl[S2CN(C4H9)(C2H5)]2, SbCl[S2CN(C4H9)(C2H5)]2, BiCl[S2CN(C7H7)(CH3)]2 terhadap S. aureus, S. epidermidis, E. aerogenes and E. coli. Kesemua empat sebatian adalah aktif terhadap S. aureus kecuali SbCl[S2CN(C2H5)(C2H4OH)]2 manakala sebatian BiCl[S2CN(C7H7)(CH3)]2 dan BiCl[S2CN(CH3)(C6H11)]2 aktif terhadap S. epidermidis dengan nilai MIC masing-masing ialah 5.0 mg/mL dan 2.5 mg/mL manakala nilai MBC 5.0 mg/mL untuk kedua-dua sebatian. Hanya sebatian BiCl[S2CN(C2H5)(C2H4OH)]2 yang aktif terhadap E. aerogenes dengan nilai MIC, 1.25 mg/mL dan nilai MBC, 10 mg/mL. Kesemua sebatian kurang aktif sebagai agen antibakteria terhadap strain E. coli.

 

Kata kunci: Ditiokarbamat, stibium(III), bismuth(III), antibakteria

 

References

1.       Marinovich, M., Viviani, B., Capra, V., Corsini, E., Anselmi, L., D’Agostino, G., Nucci, A. G., Binaglia, M., Tonini, M., Galli, C. L. 2002. Facilitation of acetylcholine signaling by the dithiocarbamate fungicide propineb. Chemical Research in Toxicology 15: 26.

2.       Hou, X. L., Ge, Z. M., Wang, T. M., Guo, W., Cui, J. R., Cheng, T. M., Lai, C. S., Li, R.T. 2006. Dithiocarbamic acid esters as anticancer agent. Part1: 4- substituted piperazine-1-carbodithioc acid 3-cyano-3,3-diphenyl-propyl esters. Bioorganic & Medicinal Chemistry Letters 16: 4214.

3.       Duan, Y. C., Zheng, Y. C., Li, X. C., Wang, M. M., Ye. X. W., Guan. Y. Y., Liu, G. Z., Zheng, J. X., Liu. H. M. 2013. Design, synthesis and antiproliferative activity studies of novel 1,2,3-triazoleedithiocarbamateeurea hybrids. European Journal of Medicinal Chemistry 64: 99-110.

4.       Halimehjani, A. Z., Marjani, K., Ashouri, A., Amani. V. 2011. Synthesis and characterization of transition metal dithiocarbamate derivatives of 1 aminoadamantane: crystal structure of (N-adamantyldithiocarbamato) nickel (II). Inorganica Chemica Acta 373: 282.

5.       Ibrahim Baba, Karimah Kassim, Yang Farina, Abdul Hamid Othman, Abdul Razak Ibrahim, Awang Usman, Hoong-Kun and Seik Weng Ng. 2002. Tris(N-butyl-N-ethyldithiocarbamato)bismuth(III). Acta Crystallographica Section E E58: m756-m757.

6.       Kean Yong Low, Ibrahim Baba, Yang Farina, A. Hamid Othman, Abdul Razak Ibrahim, Hoong-Kun Fun and Seik Weng Ng. 2001. Crystal structure of tris(2-hydroxyethylisopropyldithiocarbamato)antimony and Tris(2-hydroxyethylisopropyldithiocarbamato)bismuth hemihydrates. Main Group Metal Chemistry 4(7): 451-452.

7.       Tiekink, E. R. T. 2003. Molecular architecture and supramolecular association in the zinctriad 1,1-dithiolates. Steric control as a design element in crystal engineering. Crystal Engineering Communication 5: 101.

8.       Cui, L., Han-dong, Y., Yang, M., Quan, L., Wang, D., 2008. Catena-poly[[(N,N-diethyldithiocarbamato-κ2S:Sʹ)phenylbismuth(III)]-µ-chlorido]. Acta Crystallographica Section E 64: 1452.

9.       APEX-II and SAINT. 2000. Bruker AXS Inc., Madison, Wisconsin, USA.

10.   Sheldrick G. M. 2007. SADABS, Bruker AXS Inc., Madison, Wisconsin, USA.

11.   Sheldrick, G. M. 2008. A short history of SHELX. Acta Crystallograhica A64: 112-122.

12.    Onwudiwe, D. C., Arfin, T., Strydom, C.A., Kriek, R. J. 2013. Synthesis, spectroscopic characterization and behavior of AC impedance spectroscopy of Cd(II) bis(N para methylphenyl dithiocarbamate). Electrochimica Acta 10: 106.

13.    Zhang, R., Sun, J. & 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.

14.    Sovilj, S. P., Vučković, G., Babić, K., Sabo, T. J., Macura, S., Juranić, N. 1997. Mixed ligand complexes of cobalt(III) with dithiocarbamates and a cyclic tetradentate secondary amine. Journal of Coordination Chemistry 41: 19.

15.    Onwudiwe, D. C. & Ajibade, P. A. 2010. Synthesis and characterization of Zn(II), Cd(II), and Hg(II) alky-aryl dithiocarbamate: X-ray crystal structure of [(C6H5N(et)CS2)Hg(C6H5N(butyl)CS2)]. Synthesis Reactivity in Inorganic Metal Organic Chemistry 40: 279.

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

17.    Zheng, H., Sun, X., He, Q., Liang, K., Zhang, P. 2008. Synthesis and trapping properties of        N-dithiocarbamate macromolecule heavy-metal flocculants. Journal of Applied Polymer Science 110: 2461–2466.

18.    Singh, R. & 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.

19.    Shaheen, F., Badshah, A., Gielen, M., Dusek, M., Fejfarova, K., de Vos, D. & 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.

20.    Fuentes-Martinez, P. J., Toledo-Martiez, I., Roman-Bravo, P., Garcia, Y. G. P., Godoy-Alcantar, C., Lopez-Cardoso, M. & Morales-Rojas, H., 2009. Diorganotin(IV) dithiocarbamate complexes as chromogenic sensors of anion binding. Polyhedron 28: 3953-3966.

21.    Singh, N. & Bhattacharya, S. 2012. Synthesis and characterization of some triorgano, diorgano, monoorganotinand a triorganolead heteroaromatic dithiocarbamate complexes. Journal of Organometallic Chemistry 700: 69–77.

22.    Ajibade, P. A., Idemudia, O. G., Okoh, A. I. 2013. Synthesis, characteriazation, and antibacterial studies of metal complexes of sulfadiazine with N-alkyl-N phenyldithiocarbamate. Bulletin of the Chemical Society of Ethiopia 27(1): 77-84.

23.    Hania, M. M. 2009. Synthesis and Antibacterial Activity of Some Transition Metal Complexes of Oxime, Semicarbazone and Phenyldrazone. E-Journal of Chemistry 6:508-514.

 

 

Previous                    Content                    Next