Abstract
The crystal structures of two mixed-valence copper cyanide compounds involving N-methyl-ethylenedi-amine (meen), are described. In compound (I), poly[bis(μ3-cyanido-κ3C:C:N)tris(μ2-cyanido-κ2C:N)bis(N-methylethane-1,2-di-amine-κ2N,N')tricopper(I)copper(II)], [Cu4(CN)5(C3H10N2)2] or Cu4(CN)5meen2, cyanide groups link CuI atoms into a three-dimensional network containing open channels parallel to the b axis. In the network, two tetra-hedrally bound CuI atoms are bonded by the C atoms of two end-on bridging CN groups to form Cu2(CN)6 moieties with the Cu atoms in close contact at 2.560 (1) Å. Other trigonally bound CuI atoms link these units together to form the network. The CuII atoms, coordinated by two meen units, are covalently linked to the network via a cyanide bridge, and project into the open network channels. In the mol-ecular 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 CuII atom coordinated by two meen groups with a trigonal-planar CuI atom coordinated by CN groups. The mol-ecules are linked into centrosymmetric dimers via hydrogen bonds to two water mol-ecules. In both compounds, the bridging cyanide between the CuII and CuI atoms has the N atom bonded to CuII and the C atom bonded to CuI, and the CuII atoms are in a square-pyramidal coordination.
Highlights
The crystal structures of two mixed-valence copper cyanide compounds involving N-methylethylenediamine, are described
Two tetrahedrally bound CuI atoms are bonded by the C atoms of two end-on bridging CN groups to form Cu2(CN)6 moieties with the Cu atoms in close contact at 2.560 (1) Å
In the molecular compound (II), [(N-methylethylenediamine-2N,N0 )copper(II)]-2cyanido-2C:N-[bis(cyanido-C)copper(I)] monohydrate, [Cu2(CN)3(C3H10N2)2]H2O or Cu2(CN)3meen2H2O, a CN group connects a CuII atom coordinated by two meen groups with a trigonal–planar CuI atom coordinated by CN groups
Summary
There is continuing interest in the synthesis and structures of coordination polymers involving CuCN networks (Etaiw et al., 2015, 2016; Cai et al, 2011). The structure determinations described here arise from our ongoing syntheses of mixedvalence copper cyanide complexes incorporating various amines, with the aim of the directed synthesis of new polymeric structures. Syntheses involving N-methylethylenediamine, meen, led to the formation of blue crystals of (II), Cu2(CN)3meen2H2O, which formed as elongated plates. Their structure described here is that of a molecular compound very similar to the eten derivative referred to above. Syntheses with meen have been carried out in the presence of tetrahedral monovalent anions such as BF4 and ClO4, in the hope that incorporation of negative ions might induce crystallization of a polymeric structure. Symmetry codes: (i) x; y þ 1; z þ 12; (ii) x; y þ 1; z; (iii) x þ 12; y þ 12; z þ 12
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a call
