Use of [Re6Q8(CN)6]4- (Q = S, Se, Te) cluster anions and Cu(I) cationic complexes with 2,2′-bipyridine for the construction of new cyano-bridged coordination compounds

A series of four new coordination compounds [{Cu(bpy)(2)(mu-CN)Cu(bpy)}(2)Re6S8(CN)(6)]center dot bpy center dot 2H(2)O (1), [(Cu (bpy))(2)(mu-CN)][{Cu(bpy)}(3)Re6S8(CN)(6)] (2) and [{Cu(bpy)(mu-CN)Cu(bpy)}(2){Cu(bpy)}(2)Re(6)Q(8)(CN)(6)] (3, Q = Se; 4, Q = Te) have been synthesized by the reactions of hexanuclear rhenium(III) chalcocyanide complexes, CuCN and 2,2'-bipyridine (bpy) under hydrothermal conditions. Compound 1 was characterized by single-crystal X-ray diffraction analysis, compounds 2-4 were characterized by a set of methods, including IR spectroscopy, thermal analysis, elemental analysis, EDS, and single-crystal X-ray diffraction analysis. 1 has a molecular structure, in which two cyano groups of cluster anion [Re6S8(CN)(6)](4-) are N-bonded to the dimeric mixed-valent cations {Cu(bpy)(2)(mu-CN)Cu(bpy)}(2+) through axial coordination to the Cu+ cations. In 2, the cluster anions provide all of their six cyano groups for coordination with the copper centers of {Cu(bpy)}(+) moieties, giving rise to a 3D framework in which the cavities are occupied by the dimeric cations [(Cu(bpy)}(2)(mu-CN)](+). 3 and 4 are isostructural and have a 1D chain structure, in which four equatorial cyano groups of cluster anions are N-bonded to the {Cu(bpy)}(+) bridging fragments, while two axial cyano groups are terminated by dimeric cations (Cu(bpy)(mu-CN)Cu(bpy)}(+). The compounds synthesized appear to be the first examples which combine hexanuclear rhenium(III) chalcocyanide clusters and monovalent Cu(I) ions. (C) 2015 Elsevier Ltd. All rights reserved.