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 [Cu-3(CN)(3)(2,2'-bpy)] (1) (2,2'-bpy = 2,2'-bipyridine) and [Cu-3(CN)(3)(phen)] (2) (phen = 1, 10-phenanthroline) are similar to that of the previously reported [Cu-4(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 [Cu-3(CN)(3)(biquin)(2)] (3), [Cu-2(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.