Crystal structure of bis-(1,1,2,2-tetra-methyl-diphosphane-1,2-di-thione-κ(2) S,S')copper(I) tetra-fluorido-borate.

Peter W R Corfield,Uwe Seeler

doi:10.1107/s2056989015009913

Abstract

In the title compound, [Cu(C4H12P2S2)2]BF4, both diphosphine di-sulfide mol-ecules bind to the Cu(I) atom, as chelating ligands via the S atoms, forming a monovalent cation with a slightly distorted tetra-hedral coordination around the Cu(I) atom. The average Cu-S distance is 2.350 (15) Å, with small but possibly significant differences within each chelate ring. Ligand P=S distances average 1.964 (3) Å, and the P-P distances are 2.2262 (13) and 2.2166 (14) Å. The ligand chelate rings are twisted in opposite directions, with one in the λ and one in the δ configuration. Although the anisotropic displacement parameters of the F atoms of the anion are quite large compared to that of the B atom, difference Fourier syntheses indicate only one set of sites for the F atoms. In the crystal, possible C-H⋯F hydrogen bonds may stabilize the orientation. The B-F distances, uncorrected for libration, average 1.359 (6) Å.

Highlights

In the title compound, [Cu(C4H12P2S2)2]BF4, both diphosphine disulfide molecules bind to the CuI atom, as chelating ligands via the S atoms, forming a monovalent cation with a slightly distorted tetrahedral coordination around the CuI atom
The title compound was one of a number of phosphine sulfide copper complexes synthesized by Devon Meek and his group (Meek & Nicpon, 1965)
The tetramethyldiphosphinedisulfide ligand was shown in one case to bridge copper atoms forming a polymeric chain (Cotton et al, 1974b)

Summary

Chemical context

The title compound was one of a number of phosphine sulfide copper complexes synthesized by Devon Meek and his group (Meek & Nicpon, 1965). The tetramethyldiphosphinedisulfide ligand was shown in one case to bridge copper atoms forming a polymeric chain (Cotton et al, 1974b). Our work was initiated to verify the chelating structure that had been predicted for the present compound. We have reported this structure previously at the 1973 winter meeting of The American Crystallographic Association. The crystal structure of the corresponding hexafluoridophosphate salt has been reported by Liu et al (2003)

Structural commentary

Supramolecular features

Findings

Refinement details