A novel trinuclear cobalt complex: crystal and electronic structure of perylene bis(maleonitriledithiolato)cobaltate (Per)4[Co(mnt)2

Abstract

Single crystals of (Per)4[Co(mnt)2]3 (Per = perylene; mnt = maleonitriledithiolate) were obtained as a minor product of the electrochemical oxidation of perylene and [(n-C4H9)4N][Co(mnt)2]. The structure, solved by X-ray diffraction at room temperature, was monoclinic, space group P2(1)/n with cell parameters a = 12.093(l) angstrom, b = 20.912(1) angstrom, c = 16.633(l) angstrom, beta = 94.290(6)-degrees, V = 4194.5(5) angstrom3, and Z = 2. The crystal structure consists of [Co(mnt)2]3 units and trimers of perylene units with an extra perylene molecule placed perpendicular to this trimer. The EPR spectrum at room temperature shows a narrow (0.4 G) and almost isotropic line at g = 2.0031 ascribed to (Per)3+. Extended Huckel molecular orbital calculations on this structure support a description of this solid as [CO(Mnt)2]3-(Per)3+(Per)0.