Syntheses, crystal structures, thermal analysis, and spectra of two complexes containing bis(maleonitriledithiolate)nickelate(II) anion and di-substituted chlorobenzyl triphenylphosphinium cation

ABSTRACTTwo new ion-pair metal–bis(dithiolene) complexes, with the formulas [2,4-BiClBzTPP]2[Ni(mnt)2](1) and [2,6-BiClBzTPP]2[Ni(mnt)2](2) ([2,4-BiClBzTPP]+ = 2,4-bichlorobenzyl)triphenylphosphonium, [2,6-BiClBzTPP]+ = 2,6-bichlorobenzyl)triphenylphosphonium, and mnt2− = maleonitriledithiolate) have been synthesized and characterized by spectroscopic and physicochemical methods as well as X-ray diffraction. Two complexes crystallize in the triclinic space group P-1 and the central Ni(II) ion shows a distorted square planar coordination geometry. The anions (A) and cations (C) in complex 1 stack together into a columnar structure with ···A-CC-A-CC-A··· sequence. Lattice stability is provided by weak interactions observed in 1 and 2 such as C–H···N, C–H···Cl, C–H···S, C–H···Ni, and C–H···π hydrogen bonds which result in the forming of a 3D network structure. Thermal analysis reveals that 1 and 2 are stable up to 211°C and 208°C, respectively, and the final decomposition product of two complexes is metal ni...