Add time:07/16/2019         Source:sciencedirect.com

New bis(N-benzyl-N-substituted benzyldithiocarbamato-S,S′)nickel(II) (1–3) and (N-benzyl-N-substituted benzyldithiocarbamato-S,S′)(isothiocyanato-N)- (triphenylphosphane)nickel(II) (4–6) [where substituted benzyl = 2-HOC6H4CH2 (1,4), 3-HOC6H4CH2 (2,5), 4-FC6H4CH2 (3,6)] were synthesized and characterized using IR, electronic, and NMR (1H and 13C) spectra. X-ray structural analysis of homoleptic complex (1) and heteroleptic complexes (5 and 6) confirmed the presence of four coordinated nickel in a distorted square planar arrangement with NiS4 and NiS2PN chromophores, respectively. The νC–S stretching vibrations are observed around 990 cm−1 without any splitting supporting the bidentate coordination of the dithiocarbamate ligand. Electronic spectral studies of all the complexes (1–6) indicate that the geometry of the nickel atom is probably square planar. NMR spectra of all homoleptic and heteroleptic complexes (1–6) reveal a weak signal associated with the backbone carbon (N13CS2) in the region 204.0–210.0 ppm with a weak intensity characteristic of the quaternary carbon signals. The greater trans influence of triphenylphosphine in complexes 5 and 6 is supported by the long NiS distance compared to other NiS distance which is opposite to the NCS− ligand. In the structure of complex 5, C–H⋯π(chelate) interactions results in polymeric chain. Both structures show intramolecular Ni⋯H interactions but that on 6 is the strongest. C–H⋯π interactions are also found in 1, 5 and 6. Hirshfeld surface analysis and the associated 2D fingerprint plots of 1, 5 and 6 have been studied to evaluate intermolecular interactions. The molecular geometries of complexes 1, 5 and 6 have been optimized by abinitio HF method using LANL2DZ program.

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