Dimer formation in the crystal structure of (dithiobenzoato)(trithioperoxybenzoato)platinum(II)

Abstract

(Dithiobenzoato)(trithioperoxybenzoato)platinum(II) was obtained through reactions of [Pt₂(S₂CEt)₄] and PhC(O)SH and of K₂[PtCl₄], CF₃SO₃Ag and PhC(O)SH. It crystallizes in the monoclinic space group C2/c with a= 16.629(2), b= 6.296(1), c= 29.182(2)Å, β= 91.85(1)°, and Z= 8. The complex has four-and five-membered chelate rings with a normal square-planar PtS₄arrangement. The structure consists of dimers with a configuration in which the five-membered chelate ring of one molecule lies over the four-membered ring of the other. An extended-Hückel molecular orbital calculation suggests intradimer charge-transfer interaction as the driving force for the formation of the dimer. The diffuse reflectance spectrum of a powder sample of the complex gives new bands which are absent from the solution spectra.