Crystal Structures of Two New Complexes Produced by Reaction of Copper(I) Cyanide with Thioacetamide. In Situ Formation of the Thiosulfate Anion

Abstract

An attempt to synthesize a complex between copper(I) cyanide and thioacetamide (ta) by a direct combination in aqueous solution, surprisingly, produced instead Cu(4)(S(2)O(3))(2)(ta)(10).ta (1), a complex lacking cyanide but including thiosulfate. We know of no precedent for the production of thiosulfate from an aqueous solution of ta. Using a new synthetic approach, a complex of CuCN and ta was subsequently prepared-(CuCN)(ta), 2. In the new method, which has been found to be widely applicable to water-soluble ligands, CuCN is made "available" for coordination by dissolving it in aqueous sodium thiosulfate. Complex 1 crystallizes in the triclinic space group P&onemacr; (No. 2) with unit cell dimensions a = 10.139(3) Å, b = 12.230(4) Å, c = 12.665(4) Å, alpha = 85.20(2) degrees, beta = 67.32(2) degrees, gamma = 68.47(2) degrees, V = 1345(2) Å(3), and Z = 2. Complex 2 crystallizes in the orthorhombic space group Pna2(1) (No. 33) with unit cell dimensions a = 6.993(9) Å, b = 8.744(3) Å, c = 9.372(6) Å, V = 573(1) Å(3), and Z = 4. Some possible pathways for the production of thiosulfate are discussed.