Synthesis and characterization of [chloro{2(1H)-pyridinethione-S}{tris(pyridin-2-ylthiolato)methyl-C,N,N′,N″]}nickel(II)], [Ni(TPTM)(SPyH)Cl]

The compound, [chloro{2(1H)-pyridinethione-S}{tris(pyridin-2-ylthiolato)methyl-C,N,N′,N″]}nickel(II)], [Ni(TPTM)(SPyH)Cl], was isolated from the reaction between NiCl2 · 6H2O and tris(pyridin-2-ylthiolato)methane in aqueous EtOH. X-ray crystallography at 120 K revealed an octahedral arrangement about Ni with a tetradentate tris(pyridin-2-ylthio)methyl-C,N,N,N ligand, a monodentate 2(1H)-pyridinethione-S ligand and a chloride. The 2(1H)-pyridinethione-S ligand was derived from tris(pyridin-2-ylthio)methane probably via an acid catalysed hydrolysis reaction. Intramolecular N–H–Cl and C–H–Cl interactions help to cement the molecular structure. Weak C–H–Cl and C–H–S hydrogen bonding interactions link molecules of [Ni(TPTM)(SPyH)Cl] into a 3D array. EPR and UV spectra, and Hartree–Fock theoretical calculations are reported.