Crystal structures of two mixed-valence copper cyanide complexes withN-methylethylenediamine

Abstract

The crystal structures of two mixed-valence copper cyanide compounds involvingN-methylethylenediamine (meen), are described. In compound (I), poly[bis(μ3-cyanido-κ3C:C:N)tris(μ2-cyanido-κ2C:N)bis(N-methylethane-1,2-diamine-κ2N,N′)tricopper(I)copper(II)], [Cu4(CN)5(C3H10N2)2] or Cu4(CN)5meen2, cyanide groups link CuIatoms into a three-dimensional network containing open channels parallel to thebaxis. In the network, two tetrahedrally bound CuIatoms are bonded by the C atoms of two end-on bridging CN groups to form Cu2(CN)6moieties with the Cu atoms in close contact at 2.560 (1) Å. Other trigonally bound CuIatoms link these units together to form the network. The CuIIatoms, coordinated by two meen units, are covalently linked to the networkviaa cyanide bridge, and project into the open network channels. In the molecular compound (II), [(N-methylethylenediamine-κ2N,N′)copper(II)]-μ2-cyanido-κ2C:N-[bis(cyanido-κC)copper(I)] monohydrate, [Cu2(CN)3(C3H10N2)2]·H2O or Cu2(CN)3meen2·H2O, a CN group connects a CuIIatom coordinated by two meen groups with a trigonal–planar CuIatom coordinated by CN groups. The molecules are linked into centrosymmetric dimersviahydrogen bonds to two water molecules. In both compounds, the bridging cyanide between the CuIIand CuIatoms has the N atom bonded to CuIIand the C atom bonded to CuI, and the CuIIatoms are in a square-pyramidal coordination.