A novel ‘tent-like’ structure of a copper(I) aggregate. The crystal and molecular structure of nona[N-(diethoxythiophosphoryl)-N′-phenylisothioureato]decacopper(I) perchlorate

Abstract

The pale yellow complex formed by the reaction of copper(II) and N-(diethoxythiophosphoryl)-N′-phenylthiourea is shown to be a cationic Cu^I aggregate, [Cu₁₀{(EtO)₂P(S)–NC(S^–)NHPh}₉]⁺ Crystals were obtained with ClO₄^– as a counter ion and the structure of the aggregate was determined by X-ray diffraction. The unit cell is triclinic, space group P, with a= 16.06(1), b= 22.19(1), c= 22.455(6)Å, α= 90.16(3), β= 108.63(4), γ= 91.37(5)°, and Z= 2. The intensities of 8 903 reflections were collected (θ_max·= 18°). The final weighted residual for 7 249 reflections with I > 2σ(I) was 0.100. Each aggregate comprises: ten Cu^I atoms arranged in an approximate tetrahedron whose sides are each delineated by three Cu atoms; nine ligand molecules, each chelating one copper atom via two sulphur atoms; and one perchlorate anion neutralising the positive charge carried by a single, non-chelated copper. This Cu^I₁₀S₁₈ core represents the novel member of a family of copper–sulphur aggregates. Observed Cu–Cu distances (3.11–4.06 Å) indicate the absence of any significant metal–metal bonding. Sulphur co-ordination varies from one and two for PS centres to two and three for C–S^– groups.