Syntheses, Crystal Structures, Thermal Analysis, And Spectra Of Two Complexes Containing Bis(Maleonitriledithiolate)Nickelate(Ii) Anion And Di-Substituted Chlorobenzyl Triphenylphosphinium Cation

Two 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 mnt(2-) = 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 center dot center dot center dot A-CC-A-CC-A center dot center dot center dot sequence. Lattice stability is provided by weak interactions observed in 1 and 2 such as C-H center dot center dot center dot N, C-H center dot center dot center dot Cl, C-H center dot center dot center dot S, C-H center dot center dot center dot Ni, and C-H center dot center dot center dot pi hydrogen bonds which result in the forming of a 3D network structure. Thermal analysis reveals that 1 and 2 are stable up to 211 degrees C and 208 degrees C, respectively, and the final decomposition product of two complexes is metal nickel.