Preparation, crystal structure, and spectroscopic studies of [NPrn4]2[(PhS)CuS2MoS2] and [NPrn4]2[(PhS)CuS2MoS2Cu(SPh)], containing benzenethiolatocopper(I)–tetrathiomolybdate(VI) complex anions

Abstract

The complexes [(PhS)CuS₂MoS₂]^2– and [(PhS)CuS₂MoS₂Cu(SPh)]^2– have been prepared by the reaction of KSPh on the corresponding cyano-complex and isolated as their [NPrⁿ₄]⁺ salts. The complex [NPrⁿ₄]₂[(PhS)CuS₂MoS₂] crystallises in the space group P2₁/c with a=16.534(2), b=16.608(2), c=14,863(2)Å, β=104.60(1)°, and Z= 4, while [NPrⁿ₄]₂[(PhS)CuS₂MoS₂Cu(SPh)] crystallises in the space group C2/c with a=17.064(2), b=15.646(2), c=18.448(2)Å, β= 110.47(1)° and Z= 4. The structures were solved by Patterson and Fourier techniques from 4 495 and 2 404 diffractometer data, respectively, and refined to respective R values of 0.060 and 0.051. The anion [(PhS)CuS₂MoS₂]^2– involves an essentially tetrahedral [MoS₄]^2– moiety co-ordinated as a bidentate ligand to a copper(I) atom [Mo-S(terminal)= 2.162(6), Mo-S(Cu)= 2.221(9), Cu-S = 2.211(13), and Mo ⋯ Cu = 2.636(1)Å], the third position of the trigonal planar co-ordination about the copper being occupied by a benzenethiolate group [Cu-S = 2.188(2)Å]. The anion [(PhS)CuS₂MoS₂Cu(SPh)]^2– has crystallographic C₂ symmetry and involves the co-ordination of an essentially tetrahedral [MoS₄]^2– moiety to two copper(I) atoms [Mo-S = 2.206(6), Cu-S = 2.212(2), and Mo ⋯ Cu = 2.632(1)Å], with each trigonal planar copper(I) atom also participating in a Cu–SPh bond of length 2.171(2)Å. These structural data have been used to interpret ⁹⁵Mo and ¹H n.m.r., vibrational, and u.v.-visible spectroscopic data.