Synthesis and X-ray structure of nickel(II) benzylpiperazine-dithiocarbamate complex [Ni(bpdtc)(PPh3)2]ClO4·PPh3

A mixed-ligand nickel(II) dithiocarbamate complex of the composition [Ni(bpdtc)(PPh3)2]ClO4·PPh3 was synthesized, characterized (elemental analysis, UV-Vis, IR and NMR spectroscopy and molar conductivity measurements) and its X-ray structure was determined. The three ligands are arranged in a distorted square-planar geometry (an S2P2 donor set), with the bond lengths and angles within the vicinity of the central atom as follows: NiP = 2.2150(6) and 2.2529(6) Å, NiS = 2.2267(6) and 2.2129(6) Å, PNiP = 105.11(2)°, SNiS = 78.26(2)°. The PNiP angle of the studied complex falls outside the interval of 98.37-102.92° determined for thirteen formerly reported structural analogues involving the [Ni(ndtc)(PPh3)2]+ moiety with a combination of dithiocarbamate (ndtc) and triphenylphosphine (PPh3) ligands. In the crystal, the complex cations, perchlorate anions and PPh3 molecules of crystallization are linked through intramolecular CH⋯O and CH⋯π and intermolecular CH⋯O, CH⋯C and CH⋯π contacts to a three-dimensional architecture.