Hydrazine Carbodithioate Research Articles

Synthesis and Structure of Dimeric Copper (I) Complex from Bis[(2,2’)-dimethyl 2,2’-(1,10-phenanthroline-2,9-diyl) bis(methan-1-yl-1-ylidene)-bis(hydrazinecarbo dithioate)

Metal complex, bis[(2,2’)-dimethyl 2,2’-(1,10-phenanthrline-2,9-diyl)bis(methan-1-yl-1-ylidene)-bis(hydrazinecarrbo dithioate)copper(I)], was synthesized from the reaction of Schiff base, (2,2’)-dimethyl 2,2’-(1,10-phenanthroline-2,9-diyl)bis(methan-1-yl-1-ylidene)-bis(hydrazinecarbo dithioate) and CuCl2 at reflux condition in methanol. The copper centers of the complex appear to be reduced. This probably was facilitated by in situ oxidative formation of disulfide bond at the uncomplexed ligand moieties. Single crystal X-ray diffraction analysis reveals the distorted tetrahedral geometry around the copper centers. This compound crystallizes in the triclinic space group, P-1 with crystallographic parameters: a = 10.006(3) ?, b = 13.272(3) ?, c = 22.123(6) ?, α = 85.656(6)°, β = 81.656(6)°, γ = 73.097(5)°, μ = 1.223 mm-1 , V = 2779.5(13) ?3, Z = 2, Dc = 1.437 Mg/m3, T = 293 (2) K.

Studies on novel Cu(II) complexes of 5-(4-hydroxy-phenyl)-1,3,4-thiadiazole-2-thiol and 5-thiophen-2-yl-3H-1,3,4-oxadiazole-2-thione: Synthesis, spectral and structural characterization

Two new mixed ligand complexes, [Cu(en)2](4-hpythol)2·2H2O (4-hpythol=5-(4-hydroxy-phenyl)-1,3,4-thiadiazole-2-thiol) (2) and [Cu(en)2(5-thot)2] (5-thot=5-thiophen-2-yl-3H-1,3,4-oxadiazole-2-thione (3), have been prepared, containing en as the co-ligand. The starting ligands, potassium salts of thiohydrazide carbodithioate (RCSNHNHCSSK)/hydrazine carbodithioate (RCONHNHCSSK), underwent cyclization during the crystallization or complexation in the presence of ethylenediamine (en) and converted to 5-(4-hydroxy-phenyl)-1,3,4-thiadiazole-2-thiol and 5-thiophen-2-yl-3H-1,3,4-oxadiazole-2-thione, respectively. The metal complexes have been characterized with the aid of elemental analyses, IR, magnetic susceptibility and single crystal X-ray studies. The ligand 4-hpythol and complexes 2 and 3 crystallize in the triclinic and monoclinic systems, space group P 21/n, P1¯ and P 21/c, respectively. The ligand is present in the deprotonated thiol form in [Cu(en)2](4-hpythol)2·2H2O (2), where it is ionically bonded through the thiol sulfur atom, while potassium N′-(thiophene-2-carbonyl) hydrazinecarbodithioate after cyclization is present as the thione form in [Cu(en)2(5-thot)2] (3) and is covalently bonded through the N atom of the resulting oxadiazole-2-thione. The most noteworthy feature of 4-hpythol (1) is its existence in the thiol form in the solid state. Complex 3 show irreversible redox behavior, assignable to a M2+/M3+ one electron transfer. ESR signals were registered for complexes 2 and 3. Both complexes contain extended hydrogen bonding, providing supramolecular frameworks.

Synthesis, characterization and biological activities of 3-methylbenzyl 2-(6-methyl pyridin-2-ylmethylene)hydrazine carbodithioate and its transition metal complexes

A tridentate nitrogen-sulfur Schiff base, 3-methylbenzyl 2-(6-methylpyridin-2-ylmethylene)hydrazine carbodithioate (6mpyS3M), was synthesized by condensation of 6-methylpyridine-2-aldehyde with S-3-methylbenzyldithiocarbazate. It crystallized in space group P 21/n. It displayed intermolecular N–H···N hydrogen bonding between the α-nitrogen and the pyridyl nitrogen. The thione sulfur is in a trans position with respect to the 6-methylpyridine fragment across the C–N bond but adopts a cis position with the 3-methylbenzyl fragment through the C–S bond. Octahedral complexes containing two 6mpyS3M ligands were prepared with Cu(II), Ni(II), Zn(II) and Cd(II). 6mpyS3M and its metal complexes were assayed against selected microbes and two breast cancer cell lines. 6mpyS3M was strongly active against both cancer cell lines. Its metal complexes showed high selectivity with Cu(II), Ni(II) and Zn(II) complexes strongly active against only one of the cancer cell lines, whereas the Cd(II) complex was strongly active only against the other. Only Cu(II) and Cd(II) complexes were active against some of the bacteria.

Nickel(II) complexes of 5-phenyl and 5-furan-1,3,4-oxadiazole-2-thiones containing ethylenediamine: synthesis, spectral and X-ray characterization

The products obtained by the reactions of Ni(OAc)2·4H2O with Hpot (Hpot = 5-phenyl-1,3,4-oxadiazole-2-thione) and [K(H2fchc)] (potassium N′-(furan-2-carbonyl) hydrazine carbodithioate), on treatment with excess of ethylenediamine (en), gave mixed ligand complexes [Ni(pot)2(en)2] (1) and [Ni(fot)2(en)2] (2) (fot = 5-furan-(1,3,4)-oxadiazole-2-thione). These complexes have been characterized with the aid of elemental analyses, IR, magnetic susceptibility and single crystal X-ray studies. In both complexes, the heterocyclic ligand coordinates through oxadiazole nitrogen, and the ligand exists as the thione form. The complexes 1 and 2 have distorted octahedral geometries around the centrosymmetric Ni(II) center with trans oxadiazole ligands. Both complexes show extended hydrogen bonding to give a supramolecular framework.

Synthesis and X-ray crystallographic studies of Ni (II) and Cu (II) complexes of [5-(4-pyridyl)-1,3,4] oxadiazole-2-thione/thiol formed by transformation of N-(pyridine-4-carbonyl)-hydrazine carbodithioate in the presence of ethylenediamine

The reaction of [M(H 2L) 2] [M = Ni(II) Cu(II)] (K +H 2L − = N-(pyridine-4-carbonyl)-hydrazine carbodithioate) with excess of ethylenediamine (en) gave mixed ligand complexes [Ni(en) 2(4-pytone) 2] (4-pytone = 5-(4-pyridyl)-1,3,4-oxadiazole-2-thione), and [Cu(en) 2](4-pytol) 2·H 2O (4-pytol = 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol). The metal complexes have been characterized with the aid of elemental analyses, IR, magnetic susceptibility and single crystal X-ray studies. Complexes ( 1) and ( 2) crystallize in monoclinic system, space group P 1 21/ n 1 and C 2/ c, respectively. The ligand after cyclization is present in the deprotonated thiol form in the Cu(II) complex where it is ionically bonded through sulfur. In the Ni(II) complex ( 1) bonding of the ligand take place through oxadiazole nitrogen and the ligand exists as the thione form.

Synthesis and characterization of cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes of benzyl N-[1-(thiophen-2-yl)ethylidene] hydrazine carbodithioate and benzyl N-[1-(thiophen-3-yl)ethylidene] hydrazine carbodithioate and the X-ray crystal structure of bis{benzyl N-[1-(thiophen-2-yl)ethylidene] hydrazine carbodithioate}nickel(II)

Two bidentate Schiff bases have been synthesized by reaction of S-benzyldithiocarbazate with 2-acetylthiophene and 3-acetylthiophene to give benzyl N-[1-(thiophen-2-yl)ethylidene] hydrazine carbodithioate (SB2ATP) and benzyl N-[1-(thiophen-3-yl)ethylidene] hydrazine carbodithioate (SB3ATP). The SB2ATP and SB3ATP were then reacted with five metal ions, cobalt(II), nickel(II), copper(II), zinc(II) and cadmium (II) to form 10 metal complexes, all of general formula ML 2. The compounds synthesized were assayed for their bioactivities against selected pathogens and cancer cells. X-ray crystal structure analysis of Ni(SB2ATP) 2 showed it to be a distorted square planar complex. All the compounds are non-electrolytes in DMSO. Cu(SB2ATP) 2 showed strong activity towards Candida lypolytica. SB2ATP, SB3ATP, Co(SB2ATP) 2, Cd(SB2ATP) 2 and Cu(SB3ATP) 2 showed weak activity against several microbes and fungi while the others showed no activity toward these targets. SB2ATP and Cd(SB3ATP) 2 showed significant bioactivity towards human myeloid leukemia (HL-60) while Co(SB3ATP) 2 showed slight cytotoxic activity towards this cell line. SB2ATP, SB3ATP, Co(SB2ATP) 2, Cu(SB2ATP) 2, Cu(SB3ATP) 2, Zn(SB2ATP) 2 and Cd(SB2ATP) 2 showed significant chemotherapeutic activity against human breast carcinoma with positive estrogen receptor (MCF-7) while the remainder of the compounds showed significant bioactivity. The Schiff bases displayed higher cytotoxic activity compared to their metal complexes except for Cu(SB3ATP) 2. None of the compounds showed any cytotoxic activity towards human cervical cancer (HeLa) or towards human breast carcinoma with negative estrogen receptors (MDA-MB-231).

Reactivity of some coordinated ligands containing sulphur towards nucleophilic substitution reactions—III. Reaction of [(1-phenylethanediylidine bis-S-methylhydrazinecarbodithioate) NNS′S′(−2)] nickel(II) with primary and secondary amines and cyclization of the hydrazine derivative with β-diketones

A series of nickel(II) complexes with unsymmetric NNSS quadridentate Schiff bases containing both hydrazinecarbothioamidate and S-methylhydrazinecarbodithioate residues have been prepared by the nucleophilic displacement of one SCH 3 group from [(1-phenyl-1,2-ethanediylidine bis(S-methyl hydrazine carbodithioate) NNSS(−2)]nickel(II) with primary and secondary amines. The N-diethyl substituted complexes of palladium(II) and platinum(II) have been similarly prepared. The monohydrazine nickel(II) complex has been also prepared and its condensation with acetylacetone and benzoylacetone to the corresponding pyrazoles is also discussed. The electron impact mass spectral studies suggest the preferential displacement of the SCH 3 group on the carbon atom directly conjugated to the phenyl group. The infrared, ultraviolet and visible absorption spectra as well as the 1H NMR spectra of the newly prepared complexes are discussed.

Nickel(II) chelates of Schiff bases derived from isatin and chromone with amino acids and substituted hydrazines

Nickel(II) complexes of the Schiff base derivatives of isatin with glycine, β-alanine, anthranilic acid, S-methyl hydrazine carbodithioate, the ammonium salt of hydrazine carbodithioate, thiosemicarbazide, and benzoyl hydrazine, and nickel(II) complexes of 6-formyl-7-hydroxy-5-methoxy-2-methyl chromonelideneS-methyl hydrazine carbodithioate and benzoyl hydrazone, were prepared and characterized by elemental analysis, i.r., u.v.-vis spectra and magnetic measurements. All the complexes are octahedral.

Adduct formation by nickel(II) complexes of S-methyl hydrazine carbodithioate schiff bases with 2,2′-bipyridyl and 1,10-phenanthroline

Abstract The base-adducts of nickel(II) complexes of S-methyl hydrazine carbodithioate Schiff bases with 2,2′-bipyridyl and 1,10-phenanthroline are prepared and isolated in benzene and acetonitrile, and analysed. Structures are suggested on the basis of IR and electronic spectra. Adduct formation with 2,2′-bipyridyl has been studied in a dichloro-ethane solution, spectrophotometrically. The results obtained suggest the formation of the cis -octahedral monoadduct.