Malaysian Journal of Analytical Sciences Vol 19 No 2 (2015): 349 – 358

 

 

 

SYNTHESIS, CHARACTERISATION AND BIOLOGICAL STUDIES OF NEW PHENYLTIN(IV) DITHIOCARBAMATE COMPOUNDS

 

(Sintesis dan Kajian Biologi Sebatian Fenilstanum(IV) ditiokarbamat)

 

Amirah Faizah Abdul Muthalib1, 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 UKM Bangi, Selangor, Malaysia

 

*Corresponding author: aibi2005@gmail.com

 

 

Received: 6 November 2014; Accepted: 12 January 2015

 

 

Abstract

Nine chlorophenyltin(IV) dithiocarbamate compounds of general formula PhSnCl[S2CNR’R’’]2 (R’ = CH3, C2H5, C7H7 and R” = C2H5, C6H11, iC3H7, C7H7) were prepared in one pot reaction of various secondary amine, carbon disulphide and phenyltin(1V) trichloride with the ratio of 2:2:1. These compounds have been characterized by elemental analysis, infrared spectroscopy, ultraviolet spectroscopy, 1H, 13C NMR spectroscopy as well as single crystal X-ray crystallography. Data from X-ray crystallography showed that (C6H5)SnCl[S2CN(C2H5)(iC3H7)]2 is six coordinated bonded with two chelating dithiocarbamate ligands in bidentate fashion, methyl-C and chloride atom thus form a distorted octahedral geometry. Five selected compounds, (C6H5)SnCl[S2CN(CH3)(C2H5)]2, (C6H5)SnCl[S2CN(CH3)(C6H11)]2, (C6H5)SnCl[S2CN(C2H5)(iC3H7)]2, (C6H5)SnCl[S2CN(C7H7)(iC3H7)]2 and (C6H5)SnCl[S2CN(C7H7)2]2 were screened for anticancer activity against Chang liver cells. These compounds were demonstrated no cytotoxic effect for all concentrations under the condition of the study with no IC50 value. The minimum inhibitory concentration (MIC) and maximum bactericidal concentration (MBC) determinations for these five compounds used Escherichia coli and Pseudomonas aeruginosa as Gram negative bacteria together with Staphylococcus aureus and Staphylococcus epidermis as Gram positive bacteria. Compound (C6H5)SnCl[S2CN(CH3)(C2H5)]2 was the most active compared to the other compounds by having the lowest MIC values of 1.25 mg/mL and MBC value of 5.0 mg/mL against E. Coli and S. Aureus bacteria. Compounds (C6H5)SnCl[S2CN(C7H7)(iC3H7)]2 and (C6H5)SnCl[S2CN(C7H7)2]2 that having a benzyl group showed their MIC and MBC values slightly higher compared to the other compounds againts certain bacteria indicating their low antibacterial activities.

 

Keywords: chlorophenyltin(IV), dithiocarbamate, crystal structure, biological studies

 

Abstrak

Sembilan sebatian fenilklorostanum(IV) ditiokarbamat dengan formula sebatian PhSnCl[S2CNR’R’’]2 (R’ = CH3, C2H5, C7H7 and R” = C2H5, C6H11, iC3H7, C7H7) telah disediakan dengan sintesis secara satu pot di antara pelbagai amina sekunder, karbon disulfida dan fenilstanum(IV) triklorida dengan nisbah 2:2:1. Kesemua sebatian ini telah dicirikan dengan kaedah analisis unsur, spektroskopi inframerah, spektroskopi ultralembayung, spektroskopi NMR 1H, 13C dan kristalografisinar-X. Data daripada kristalografi sinar-X menunjukkan struktur sebatian (C6H5)SnCl[S2CN(C2H5)(iC3H7)]2  adalah enam koordinatan dan terikat dengan dua ligan ditiokarbamat yang terkelat secara bidentat, metil-C dan atom klorida untuk membentuk geometri oktahedron terherot. Lima sebatian pilihan iaitu (C6H5)SnCl[S2CN(CH3)(C2H5)]2, (C6H5)SnCl[S2CN(CH3)(C6H11)]2, (C6H5)SnCl[S2CN(C2H5)(iC3H7)]2, (C6H5)SnCl[S2CN(C7H7)(iC3H7)]2 dan (C6H5)SnCl[S2CN(C7H7)2]2 telah disaring untuk aktiviti antikanser terhadap sel hati Chang. Sebatian ini tidak menunjukkan sebarang kesan sitotoksik pada setiap kepekatan dan tidak mempunyai nilai IC50. Ujian penentuan nilai kepekatan perencatan minimum (MIC) dan nilai kepekatan minimum bakterisidal (MBC) untuk lima sebatian ini telah menggunakan Escherichia coli dan Pseudomonas aeruginosa sebagai bakteria Gram negatif serta Staphylococcus aureus dan Staphylococcus epidermis sebagai bakteria Gram positif. Sebatian (C6H5)SnCl[S2CN(CH3)(C2H5)]2 adalah paling aktif berbanding sebatian lain dengan mempunyai nilai MIC yang terendah iaitu 1.25 mg/mL dan nilai MBC 5.0 mg/mL terhadap bakteria Escherichia coli dan Staphylococcus aureus. Sebatian (C6H5)SnCl[S2CN(C7H7)(iC3H7)]2 dan (C6H5)SnCl[S2CN(C7H7)2]2 yang mengandungi kumpulan benzil menunjukkan nilai MIC dan MBC yang lebih tinggi berbanding sebatian lain terhadap beberapa jenis bakteria dan menunjukkan aktiviti antibakteria yang lebih rendah.

 

Kata kunci: fenilklorostanum(IV), ditiokarbamat, struktur hablur, kajian biologi

 

References

1.       Coucouvanis, D. &  Fackler,  J.P.Jr.  (1976).  Square-planar  Sulphur  Compounds Inorganic  Chem.  6: 2047-2053.

2.       Cvek, B., Milacic, V., Taraba, J. & Dou, Q.P. (2008). Ni(II), Cu(II), and Zn(II) diethyldithiocarbamate compounds show various activities against the proteasome in breast cancer cells. J. Med. Chem. 51: 6256 – 6258.

3.       Rehman, Z., Muhammad, N., Ali, S., Butler, I.S. & Meetsma, A. (2011). New mononuclear organotin(IV) 4-benzhydrylpiperazine-1-carbodithioates: Synthesis, spectroscopic characterization, X-ray structures and in vitro antimicrobial activities. Inorg. Chim. Acta. 373: 187-194.

4.       Rehman, A., Hussain, M., Rehman, Z., Rauf, A., Nasim., F.H., Tahir, A.A. & Ali, S. (2010). New tetrahedral, square-pyramidal, trigonal-bipyramidal and octahedral organotin(IV) 4-ethoxycarbonylpiperazine-1-carbodithioates: Synthesis, structural properties and biological applications. J. Organomet. Chem. 695: 1526-1532

5.       Khan, H.N., Ali, S., Shahzadi, S., Sharma, A.K. & Qanungo, K. (2010). Synthesis, spectroscopy, semiempirical, phytotoxicity, antibacterial, antifungal, and cytotoxicity of diorganotin(IV) compound derived from Bu2Sn(Acac)2 and 4-methyl-1-piperidinecarbodithioic acid. Russ. J. Coord. Chem. 36: 310-316.

6.       Tiekink, E.R.T. (2008). Tin dithiocarbamates: applications and structures. Applied Organometallic Chemistry. 22: 533-550.

7.       Okoro, H.K., Fatoki, O.L., Adekola, F.A., Ximba, B.J. & Snyman, R.G. (2011). Sources, environmental levels and toxicity of organotin in marine environment- A review. Asian Journal of Chemistry. 23(2): 473-482.

8.       Hoch, M. (2001). Organotin compounds in the environment — an overview. Applied Geochemistry. 16: 719–743.

9.       Singh, K., Puri, P. & Dharampal, D. (2010). Synthesis and spectroscopic studies of some new organometallic chelates derived from bidentate ligands. Turkish Journal of Chemistry. 34:499–507.

10.    Gerasimchuk, N.N., Maher, T., Durham, P., Domasevitch, K.V., Wilking, J. & Mokhir, A. (2007). Tin(IV) Cyanoximates: Synthesis, Characterization, and Cytotoxicity. Inorganic Chemistry. 46: 7268-7284.

11.    Pallerito, L. & Nagy, L. (2002). Organotin(IV)n+ compounds formed with biologically active ligands: equilibrium and structural studies, and some biological aspects. Coordination Chemistry Reviews. 224: 111–150.

12.    Dubey, S.K.  Roy, U. (2003). Biodegradation of tri-butyltins (Organotins) by marine bacteria. Applied Organometallic Chemistry. 17: 3-8.

13.    Lou, W., Chen, M., Wang, X. & Liu, W. (2007). Size Control of monodisperse copper sulfide faceted nanocrystals and triangular nanoplates. Phys. Chem. C. 111: 9658-9663.

14.    Tiekink, E.R.T. (2008). Tin dithiocarbamates: applications and structures. Applied Organometallic Chemistry. 22: 533-550.

15.    Szolar, O.H.J. (2007). Environmental and pharmaceutical analysis of dithiocarbamates. Analytica Chimica Acta. 582: 191–200.

16.    Chengyong, S., Tang, N., Tan, M., Liu, W. & Gan, X. (1996). Synthesis and spectroscopic properties of light lanthanide monoalkyl dithiocarbamate compounds. Polyhedron. 15(1): 73-77.

17.    Mitchell, P.C.H. & Taylor, M.G. (1982). Binding of some first-row transition metal ions by a poly(iminoethylene)dithiocarbamate copolymer. Polyhedron. 1(3): 225-231.

18.    Nami, S. & Siddiqi, K.S. (2005). Convenient one-pot synthesis of symmetrical dithiocarbamates. Synthesis and reactivity in inorganic, metal-organic, and nano-metal chemistry. 34: 1581-1590.

19.    Mohamed, G.G., Ibrahim, N.A. & Attia A.E.H. (2009). Synthesis and antifungal activity of some transition metal compounds with benzimidazole dithiocarbamate ligand. Spectrochimica Acta part A. 72: 610-615.

20.    Husaina, A., Nami, S. A.A. & 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.

21.    Sharma, J., Singh, Y., Bohra, R. & Rai, A. K. (1996). Synthesis and spectral studies of diorganotin heterocyclic dithiocarbamate compounds: The crystal structure of (CH3)2Sn[S2CNCH2CH2CH2CH2CH2]2. Polyhedron. 15(7): 1097-1102.

22.    Prakasam, B.A., Ramalingam, K., Bocelli, G. & Cantoni, A. (2007). NMR and fluorescence spectral studies on bisdithiocarbamates of divalent Zn, Cd and their nitrogenous adducts: Single crystal X-ray structure of (1,10-phenanthroline)bis(4-methylpiperazinecarbodithioato) zinc(II). Polyhedron. 26:4489–4493.

23.    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) compounds with dithiocarbamate ligands: X-ray structure of bis(dibenzyl-1-S:S0-              dithiocarbamato)Pd(II). Journal of Organometallic Chemistry. 692: 3019–3026.

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

25.    Mishra, A.K., Manav, N. & Kaushik, N. K. (2005). Organotin(IV) compounds of thiohydrazones: Synthesis, characterizationand antifungal study. Spectrochim. Acta, Part A. 61:3097-3101.

26.    Sharma, R. & Kaushik, N.K. (2004). Thermal studies on some organotin(IV) compounds with piperidine and 2-aminopyridine dithiocarbamate. J. Therm. Anal. Calorim. 78:953-964.

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

28.    Seth, N., Gupta, V.D., Noth, H. & Thomann, M. (1992). Synthesis and molecular structure of tin(IV) 1-pyrrolecarbodithioates. Chemische Berichte. 125(7): 1523-1528.

29.    Harrison, P.G, Mangia, A. (1976). Structural studies in main group chemistry : XVII. The crystal and molecular structure of phenylchlorobis(diethyldithiocarbamato)tin(IV). J. Organomet. Chem, 120: 211.

30.    Li, Y.-X., Zhang, R.-F. & Ma, C.-L. (2005). Chlorobis(N,N-di-n-butyldithiocarbamato)phenyltin(IV). Acta cryst. E61: 2365

31.    Clarke, D.J., Dakternieks, D. & Tiekink, E.R.T. (2001). X-ray structure of chlorobis-(diisobutyldithiocarbamato)phenyltin(IV). Main Group Met. Chem. 24(5): 303.

32.    Boyer, I.J. (1989). Toxicity of dibutyltin, tributyltin and other organotin compounds to human and experimental animals. Toxicology. 55: 253-98. 

 

Previous                    Content                    Next