Md. Tofazzal Hossain Tarafder

Biological activity of palladium(II) and platinum(II) complexes of the acetone Schiff bases of S-methyl- and S-benzyldithiocarbazate and the X-ray crystal structure of the [Pd(asme)2] (asme=anionic form of the acetone Schiff base of S-methyldithiocarbazate) complex.

Palladium(II) and platinum(II) complexes of general empirical formula, [M(NS)(2)] (NS=uninegatively charged acetone Schiff bases of S-methyl- and S-benzyldithiocarbazate; M=Pt(II) and Pd(II)) have been prepared and characterized by a variety of physicochemical techniques. Based on conductance, IR and electronic spectral evidence, a square-planar structure is assigned to these complexes. The crystal and molecular structure of the [Pd(asme)(2)] complex (asme=anionic form of the acetone Schiff base of S-methyldithiocarbazate) has been determined by X-ray diffraction. The complex has a distorted cis-square planar structure with the ligands coordinated to the palladium(II) ions as uninegatively charged bidentate NS chelating agents via the azomethine nitrogen and the mercaptide sulfur atoms. The distortion from a regular square-planar geometry is attributed to the restricted bite angles of the ligands. Antimicrobial tests indicate that the Schiff bases exhibit strong activities against the pathogenic bacteria, Bacillus subtilis (mutant defective DNA repair), methicillin-resistant Staphylococcus aureus, B. subtilis (wild type) and Pseudomonas aeruginosa and the fungi, Candida albicans (CA), Candida lypotica (2075), Saccharomyces cerevisiae (20341) and Aspergillus ochraceous (398)-the activities exhibited by these compounds being greater than that of the standard antibacterial and antifungal drugs, streptomycin and nystatin, respectively. The palladium(II) and platinum(II) complexes are inactive against most of these organisms but, the microbe, Pseudomonas aeruginosa shows strong sensitivity to the platinum(II) complexes. Screening of the compounds for their cytotoxicities against T-lymphoblastic leukemia cancer cells has shown that the acetone Schiff base of S-methyldithiocarbazate (Hasme) exhibits a very weak activity, whereas the S-benzyl derivative (Hasbz) is inactive. However, the palladium(II) complexes exhibit strong cytotoxicities against this cancer; their activities being more than that of the standard anticancer drug, tamoxifen. The [Pt(asme)(2)] complex exhibits a very weak cytotoxicity, whereas [Pt(asbz)(2)] is inactive against leukemic cells.

Coordination chemistry and bioactivity of Ni2+, Cu2+, Cd2+ and Zn2+ complexes containing bidentate Schiff bases derived from S-benzyldithiocarbazate and the X-ray crystal structure of bis[S-benzyl-β-N-(5-methyl-2-furylmethylene)dithiocarbazato]cadmium(II)

New bidentate isomeric NS and NS′ Schiff bases were derived from the condensation of S-benzyldithiocarbazate (SBDTC) with 5-methyl-2-furyldehyde and 2-furyl-methylketone. Reaction of NS ligand with Ni(II), Cu(II), Cd(II) and Zn(II) salts gave solid complexes. Only the Ni(II) complex of the NS′ ligand was isolated. All complexes were characterized by a variety of physico-chemical techniques, viz. elemental analyses, molar conductivity, i.r. and electronic spectral studies. The Schiff bases behaved as uninegatively charged bidentate ligands. Square-planar structures have been proposed for the Cu(II) complex containing the NS Schiff base ligand and the Ni(II) complexes of the bidentate NS and NS′ Schiff base ligands. Single crystal X-ray diffraction study of [Cd(NS)2] showed that the complex was bis chelated with a distorted tetrahedral structure. The antimicrobial properties of the Schiff bases and their metal complexes indicate that the organic compounds are stronger antifungal agents than their complexes with the metals studied. However, the zinc complex of the Schiff base, S-benzyl-β-N-(5-methyl-2-furyl)methylenedithiocarbazate, (NS), was found to be highly active against CEM-SS (Human cell T-lymphoblastic leukemia) with a CD50 value of 2.0 μg cm−3, while [Cd(NS)2] was moderately active with a CD50 value of 4.95 μg cm−3. None of the compounds were found to be active against HT-29 (Human colon adenocarcinoma cells). The bioactivity of a previously reported tridentate NNS Schiff base (SBD1) and its metal complexes with nickel(II) and copper(II) are also discussed.

Coordination chemistry and bioactivity of some metal complexes containing two isomeric bidentate NS schiff bases derived from S-benzyldithiocarbazate and the x-ray crystal structures of S-benzyl-β-N-(5-methyl-2-furylmethylene)dithiocarbazate and bis[S-benzyl-β-N-(2-furylmethylketone)dithiocarbazato]cadmium(II)

Abstract Isomeric bidentate ligands having nitrogen–sulfur donor sequence were prepared by condensing S-benzyldithiocarbazate (SBDTC) with 5-methyl-2-furyladehyde (NS) and 2-furylmethylketone (NS′). Complexes of these ligands with lead, tin, iron, cobalt and cadmium gave complexes of [M(L)2] (M=Pb, Fe and Cd) and [M(L)2]Cln (M=Sn, n=2 and Co, n=1) (L=NS and NS′). The compounds have been characterized by spectroscopic studies (infrared, 1H NMR and electronic spectra). X-ray crystallographic analysis of S-benzyl-β-N-(5-methyl-2-furylmethylene)dithiocarbazate shows the presence of two independent molecules in the asymmetric unit. The molecule adopts a trans–cis configuration, as was observed in other analogues, such as SBDTC where the furylmethylene and benzyl groups are trans and cis about the NC and CS bonds, respectively. The molecular structure of bis[S-benzyl-β-N-(2-furylmethylketone)dithiocarbazato]cadmium(II) shows a tetrahedral geometry about the central cadmium atom with the bidentate ligand coordinating through the thioketo sulfur and the azomethine nitrogen atoms. The lead(II) complex of the NS ligand was highly cytotoxic against leukemic cells (CEM-SS) with a CD50 of 3.25 μg cm−3 while antimicrobial screening showed that the [Fe(NS)2]Cl2·H2O complex was effective against Aspergillus achraceous.

Coordination chemistry and biological activity of nickel(II) and copper(II) ion complexes with nitrogen–sulphur donor ligands derived from S-benzyldithiocarbazate (SBDTC)

A bidentate and a quadridentate Schiff base having NS and NNSS donor sequences were prepared by condensing S-benzyldithiocarbazate (NH2NHCSSCH2Ph) with 2,3-butanedione (1:1 and 1:2 mole ratio). NiII and CuII complexes of these ligands were studied and characterised by elemental analyses and various physico-chemical techniques. The nickel complexes, [Ni(NS)2] and [Ni(SNNS)], were diamagnetic with square-planar and five-coordinate structures, respectively. The copper complex was, however, pentacoordinated. The ligands and the complexes were screened for anticancer activity against T-lymphoblastic leukemic cells (CEM-SS) and colon cancer cells (HT-29). The NS Schiff base was strongly active against leukemic cells with a CD50 value of 2.05 μg cm−3. The nickel and copper complexes were found to be stronger antioxidants than Vitamin E.

trans–cis S-Benzyl dithiocarbazate

In the crystal structure of the title compound, C(8)H(10)N(2)S(2), the molecules are linked by N-H.S hydrogen bonds between the imino group and the thione-S atoms to form a chain along the b axis. The dithiocarbazate moiety is rotated by 85.8 (2) degrees with respect to the phenyl ring.

Magnetic, spectroscopic and biological properties of copper(II) complexes of the tridentate ligand, α-N-methyl-S-methyl-β-N-(2-pyridyl)methylenedithiocarbazate(NNS) and the X-ray crystal structure of the [Cu(NNS)I2] complex

Copper(II) complexes of general formula, Cu(NNS)X2 · nH2O (NNS = the 2-formylpyridine Schiff base of N-methyl-S-methyldithiocarbazate; X = Cl−, Br−, I−, NCS−; n = 0, 2) have been synthesized and characterized by elemental analysis and by magnetic and spectroscopic techniques. Based on magnetic and spectroscopic data, a monomeric five-coordinate square-pyramidal structure is assigned to these complexes. The crystal and molecular structure of [Cu(NNS)I2] has been determined by X-ray diffraction. The complex has a monomeric square-pyramidal structure with the ligand coordinated to the copper(II) ion via the pyridine nitrogen atom, the azomethine nitrogen atom and the thione sulfur atom. The fourth and fifth coordination sites are occupied by the iodide ligands. Antimicrobial tests indicate that Schiff base is inactive against the bacteria, Bacillus subtilis (mutant defective DNA repair), Pseudomonas aeruginosa, methicillin resistant Staphylococcus aureus and Bacillus subtilis (wild type) and weakly active against the fungi, Candida albicans, Candida lypolytica, Saccharomyces cereviseae and Aspergillus ochraceous but its copper(II) complexes, Cu(NNS)X2 are strongly active against these organisms. A cytotoxicity study of the compounds against leukemic and cervical cancer cells showed that the Schiff base is inactive, but the complexes, [Cu(NNS)I2] and [Cu(NNS)(NCS)2] · 2H2O exhibit significant activity against cervical cancer cells with CD50 values of 4.8 and 4.2 μg, respectively.