Solid state coordination chemistry: Ligand influences on the structures of one-dimensional copper(I) cyanide-organodiimine solids

The structural consequences of introducing sterically demanding substituents have been investigated for composite organic-inorganic materials of the copper cyanide-organodiimine system. The hydrothermal reactions of copper(I) cyanide and KCN, with the appropriate chelating organodiimine ligands yield a series of one-dimensional copper cyanide chains decorated either with linear {(LL)Cu(CN)} (LL = organodiimine) side chains or with diimine ligands bound directly to the copper sites of the parent chain. The structures of [Cu₃(CN)₃(2,2′-bpy)] (1) (2,2′-bpy = 2,2′-bipyridine) and [Cu₃(CN)₃(phen)] (2) (phen = 1,10-phenanthroline) are similar to that of the previously reported [Cu₄(CN)₄(biquin)] (biquin = 2,2′-biquinoline), exhibiting the characteristic one-dimensional {Cu(CN)} chain with diimine-copper cyanide side arms. In contrast, the structures of [Cu₃(CN)₃(biquin)₂] (3), [Cu₂(CN)₂(dpbp)], (4) (dpbp = 4,4′-diphenyl-2,2′-bipyridine), and [Cu(CN)(dpphen)] (5) (dpphen = 4,7-diphenyl-1,10-phenanthroline) are characterized by direct attachment of the organodiimine ligand to the copper cyanide chain.