Poly[tetraamminecopper(II) bis[tris(μ2-cyanido-κ2C,N)dicuprate(I)]]: a unique CuI–CuIImixed-valence complex containing anionic cuprous cyanide layers and [Cu(NH3)4]2+cations
The title compound, {[Cu(NH3)4][Cu(CN)3]2}n, features a CuI–CuIImixed-valence CuCN framework based on {[Cu2(CN)3]−}nanionic layers and [Cu(NH3)4]2+cations. The asymmetric unit contains two different CuIions and one CuIIion which lies on a centre of inversion. Each CuIion is coordinated to three cyanide ligands with a distorted trigonal–planar geometry, while the CuIIion is ligated by four ammine ligands, with a distorted square-planar coordination geometry. The interlinkage between CuIions and cyanide bridges produces a honeycomb-like {[Cu2(CN)3]−}nanionic layer containing 18-membered planar [Cu(CN)]6metallocycles. A [Cu(NH3)4]2+cation fills each metallocyclic cavity within pairs of exactly superimposed {[Cu2(CN)3]−}nanionic layers, but there are no cations between the layers of adjacent pairs, which are offset. Pairs of N—H...N hydrogen-bonding interactions link the N—H groups of the ammine ligands to the N atoms of cyanide ligands.