μ-Cyanido-κ²C:N-dicyanido-κ²C-bis(N-ethylethylenediamine-κ²N,N′)copper(II)copper(I)

Abstract

In the title complex, [CuICuII(CN)3(C4H12N2)2], the CuI and CuII ions and a bridging cyanide group lie on a twofold rotation axis. The CuII ion is in a slightly-distorted square-pyramidal coordination environment, with the N atoms of the two symmetry-related N-ethyl­ethylenedi­amine ligands occupying the basal positions and an N-bonded cyanide group in the apical position. The CuI ion is in a trigonal-planar coordination environment, bonded to the C atom of the bridging cyanide group and to two terminal cyanide groups. In the crystal, N—H⋯N hydrogen bonds involving two of the symmetry-unique N—H groups of the N-ethyl­ethylenedi­amine ligands and the N atoms of the terminal cyanide ligands link the mol­ecules into strands along [010].

Poly[diethylammonium [tetra-μ2-cyanido-κ8 C:N-tricuprate(I)]], a two-dimensional network solid

“…Crystals began to form after one week and were harvested as conglomerates of thick, yellow-green plates several weeks later. The intent had been to prepare a mixed-valence compound similar to those prepared from bidentate amines (Corfield & Michalski, 2014;Corfield & Sabatino, 2017) and to use the fivefold excess of base to stabilize any Cu II formed by air-oxidation. However, no crystalline mixed-valence compounds containing the base were obtained in this and similar preparations with diethylamine.…”

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

“…Cu atoms are 0.122 (1) and 0.220 (1) Å from the best plane through the amine N atoms in (I) and (II), respectively. In (I), the Cu-NH(CH 3 ) bonds are 0.05-0.07 Å longer than the Cu-NH 2 bonds (Table 1), whereas the corresponding bond lengths are more similar in (II)( Table 2), as also seen in the N-ethyl complex corresponding to (II), Cu 2 (CN) 3 eten 2 (Corfield & Michalski, 2014).…”

“…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. A variety of crystal structures form from Cu I,II -cyanide-multidentate amine systems, ranging from the classic three-dimensional mixed-valence structure Cu 3 (CN) 4 en 2 ÁH 2 O where en is ethylenediamine (Williams et al, 1972) to molecular compounds such as Cu 2 (CN) 3 eten 2 (Corfield & Michalski, 2014), where eten is N-ethylethylenediamine. Syntheses involving N-methylethylenediamine, meen, led to the formation of blue crystals of (II), Cu 2 (CN) 3 meen 2 ÁH 2 O, which formed as elongated plates.…”