Synthesis, spectral characterization and antiproliferative activity of new organotin (IV) dithiocarbamate compounds on K562 cells.

Four new organotin(IV) dithiocarbamate compounds with general formulae of PhnSn [S2CN(CH2CH2OCH2CH3)]4-n for compound 1 and 2; and PhnSn[S2CN(CH3)(CH2CH2C6H5)]4-n for compound 3 and 4 were successfully synthesized via in situ insertion method. These compounds namely, diphenyltin(IV)- [1] and triphenyltin(IV) N,N-bis(2-ethoxyethyl)dithiocarbamate [2], diphenyltin(IV)- [3] and triphenyltin(IV) N-methyl-N-phenethyldithiocarbamate [4] were each characterized with CHNS elemental analysis, FT-IR and NMR spectroscopies (1H, 13C and 119Sn). The compounds were then assessed for their cytotoxicity against K562 cells using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazholium bromide (MTT) assay upon 24 h treatment. All compounds produced the essential IR absorption bands and displayed important NCS2 peak in 13C NMR spectroscopy. From the cytotoxicity studies using MTT assay, the compounds were shown to inhibit cell proliferation in K562 leukemic cells with IC50 values ranging from 1.48 to 4.52 µM, and in the manners more cytotoxic compared to standard used imatinib.

Synthesis and cytotoxic activity of organotin(IV) diallyldithiocarbamate compounds as anticancer agent towards colon adenocarcinoma cells (HT-29).

CONTEXT: Diphenyltin(IV) diallyldithiocarbamate compound (Compound 1) and triphenyltin(IV) diallyldithiocarbamate compound (Compound 2) are two newly synthesised compounds of organotin(IV) with diallyldithiocarbamate ligands. OBJECTIVE: To assess the cytotoxic effects of two synthesised compounds against HT-29 human colon adenocarcinoma cells and human CCD-18Co normal colon cells. MATERIALS AND METHODS: Two successfully synthesised compounds were characterised using elemental (carbon, hydrogen, nitrogen, and sulphur) analysis, Fourier-Transform Infrared (FTIR), and 1H, 13C 119Sn Nucleus Magnetic Resonance (NMR) spectroscopies. The single-crystal structure of both compounds was determined by X-ray single-crystal analysis. The cytotoxicity of the compounds was assessed using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazholium bromide (MTT) assay upon 24 h of treatment. While the mode of cell death was determined based on the externalisation of phosphatidylserine using a flow cytometer. RESULTS: The elemental analysis data of the two compounds showed an agreement with the suggested formula of (C6H5)2Sn[S2CN(C3H5)2]2 for Compound 1 and (C6H5)3Sn[S2CN(C3H5)2] for Compound 2. The two major peaks of infrared absorbance, i.e., ν(C = N) and ν(C = S) were detected at the range of 1475-1479 cm-1 and 972-977 cm-1, respectively. The chemical shift of carbon in NCS2 group for Compound 1 and 2 were found at 200.82 and 197.79 ppm. The crystal structure of Compound 1 showed that it is six coordinated and crystallised in monoclinic, P21/c space group. While the crystal structure of Compound 2 is five coordinated and crystallised in monoclinic, P21/c space group. The cytotoxicity (IC50) of the two compounds against HT-29 cell were 2.36 µM and 0.39 µM. Meanwhile, the percentage of cell death modes between 60% and 75% for compound 1 and compound 2 were mainly due to apoptosis, suggesting that both compounds induced growth arrest. CONCLUSION: Our study concluded that the synthesised compounds showed potent cytotoxicity towards HT-29 cell, with the triphenyltin(IV) compound showing the highest effect compared to diphenyltin(IV).

Crystal structures and Hirshfeld surface analyses of (N-hexyl-N-methyl-dithio-carbamato-κ2S,S')triphenyl-tin(IV) and [N-methyl-N-(2-phenyl-ethyl)-dithio-carbamato-κ2S,S']tri-phenyl-tin(IV).

The crystal and mol-ecular structures of two tri-phenyl-tin di-thio-carbamate compounds, viz. [Sn(C6H5)3(C8H16NS2)], (I), and [Sn(C6H5)3(C10H12NS2)], (II), are described. The di-thio-carbamate ligand in each mol-ecule coordinates in an asymmetric fashion resulting in heavily distorted tetra-hedral C3S coordin-ation geometries for the Sn atoms, with the distortions traced to the close approach of the non-coordinating thione-S atom. The mol-ecular packing in both compounds features C-H⋯π(Sn-phen-yl) inter-actions. In (I), the donors are Sn-phenyl-C-H groups leading to centrosymmetric aggregates, while in (II), the donors are both Sn-phenyl-C-H and methyl-C-H groups leading to supra-molecular chains propagating along the b axis. The identified aggregates assemble into their respective crystals with no directional inter-actions between them. An analysis of the Hirshfeld surfaces show distinctive patterns, but an overwhelming predominance (>99% in each case) of H⋯H, C⋯H/H⋯C and S⋯H/H⋯S contacts on the respective Hirshfeld surface.

Crystal structures and Hirshfeld surface analyses of bis-[N,N-bis-(2-meth-oxy-eth-yl)di-thio-carbamato-κ2S,S']di-n-butyl-tin(IV) and [N-(2-meth-oxy-eth-yl)-N-methyl-dithio-carbamato-κ2S,S']tri-phenyl-tin(IV).

The crystal and mol-ecular structures of the two title organotin di-thio-carbamate compounds, [Sn(C4H9)2(C7H14NO2S2)2], (I), and [Sn(C6H5)3(C5H10NOS2)], (II), are described. Both structures feature asymmetrically bound di-thio-carbamate ligands leading to a skew-trapezoidal bipyramidal geometry for the metal atom in (I) and a distorted tetra-hedral geometry in (II). The complete mol-ecule of (I) is generated by a crystallographic twofold axis (Sn site symmetry 2). In the crystal of (I), mol-ecules self-assemble into a supra-molecular array parallel to (10-1) via methyl-ene-C-H⋯O(meth-oxy) inter-actions. In the crystal of (II), supra-molecular dimers are formed via pairs of weak phenyl-C-H⋯π(phen-yl) contacts. In each of (I) and (II), the specified assemblies connect into a three-dimensional architecture without directional inter-actions between them. Hirshfeld surface analyses confirm the importance of H⋯H contacts in the mol-ecular packing of each of (I) and (II), and in the case of (I), highlight the importance of short meth-oxy-H⋯H(but-yl) contacts between layers.

Di-n-butyl-bis-[N-(2-meth-oxy-eth-yl)-N-methyl-dithio-carbamato-κ2S,S']tin(IV): crystal structure and Hirshfeld surface analysis.

The complete mol-ecule of the title compound, [Sn(C4H9)2(C5H10NOS2)2], is generated by a crystallographic mirror plane, with the SnIV atom and the two inner methyl-ene C atoms of the butyl ligands lying on the mirror plane; statistical disorder is noted in the two terminal ethyl groups, which deviate from mirror symmetry. The di-thio-carbamate ligand coordinates to the metal atom in an asymmetric mode with the resulting C2S4 donor set defining a skew trapezoidal bipyramidal geometry; the n-butyl groups are disposed to lie over the longer Sn-S bonds. Supra-molecular chains aligned along the a-axis direction and sustained by methyl-ene-C-H⋯S(weakly coordinating) inter-actions feature in the mol-ecular packing. A Hirshfeld surface analysis reveals the dominance of H⋯H contacts in the crystal.

[N-Benzyl-N-(2-phenyl-eth-yl)di-thio-carbamato-κ2S,S']tri-phenyl-tin(IV) and [bis-(2-meth-oxy-eth-yl)di-thio-carbamato-κ2S,S']tri-phenyl-tin(IV): crystal structures and Hirshfeld surface analysis.

The crystal and mol-ecular structures of two tri-phenyl-tin di-thio-carbamates, [Sn(C6H5)3(C16H16NS2)], (I), and [Sn(C6H5)3(C7H14NO2S2)], (II), are described. In (I), the di-thio-carbamate ligand coordinates the SnIV atom in an asymmetric manner, leading to a highly distorted trigonal-bipyramidal coordination geometry defined by a C3S2 donor set with the weakly bound S atom approximately trans to one of the ipso-C atoms. A similar structure is found in (II), but the di-thio-carbamate ligand coordinates in an even more asymmetric fashion. The packing in (I) features supra-molecular chains along the c axis sustained by C-H⋯π inter-actions; chains pack with no directional inter-actions between them. In (II), supra-molecular layers are formed, similarly sustained by C-H⋯π inter-actions; these stack along the b axis. An analysis of the Hirshfeld surfaces for (I) and (II) confirms the presence of the C-H⋯π inter-actions but also reveals the overall dominance of H⋯H contacts in the respective crystals.

Distinct coordination geometries in bis-[N,N-bis-(2-meth-oxy-eth-yl)di-thio-carbamato-κ(2) S,S']di-phenyltin(IV) and bis-[N-(2-meth-oxy-eth-yl)-N-methyl-dithio-carbamato-κ(2) S,S']di-phenyl-tin(IV): crystal structures and Hirshfeld surface analysis.

The crystal and mol-ecular structures of two di-phenyl-tin bis-(di-thio-carbamate)s, [Sn(C6H5)2(C5H10NOS2)2], (I), and [Sn(C6H5)2(C7H14NO2S2)2], (II), are described. In (I), in which the metal atom lies on a twofold rotation axis, the di-thio-carbamate ligand coordinates with approximately equal Sn-S bond lengths and the ipso-C atoms of the Sn-bound phenyl groups occupy cis-positions in the resulting octa-hedral C2S4 donor set. A quite distinct coordination geometry is noted in (II), arising as a result of quite disparate Sn-S bond lengths. Here, the four S-donors define a trapezoidal plane with the ipso-C atoms lying over the weaker of the Sn-S bonds so that the C2S4 donor set defines a skewed trapezoidal bipyramid. The packing of (I) features supra-molecular layers in the ab plane sustained by methyl-ene-C-H⋯π(Sn-ar-yl) inter-actions; these stack along the c-axis direction with no specific inter-actions between them. In (II), supra-molecular chains along the b-axis direction are formed by methyl-ene-C-O(ether) inter-actions; these pack with no directional inter-actions between them. A Hirshfeld surface analysis was conducted on both (I) and (II) and revealed the dominance of H⋯H inter-actions contributing to the respective surfaces, i.e. >60% in each case, and other features consistent with the description of the mol-ecular packing above.