Solid state coordination chemistry of the copper(I)-cyano-organodiimine system. Two- and three-dimensional copper cyanide phases incorporating lineardipodal ligands

A series of composite inorganic-organic materials from the copper/cyanide/o rganoimine system have been isolated and structurally characterized. The st ructural consequences of introducing sterically demanding substituents and of expanding the donor to donor distance in linear dipodal organodiimine li gands has been addressed, exploiting the bridging bidentate ligands pyrazin e (pyr), 2-methylpyrazine (mpyr), 2-ethylpyrazine (etpyr), 2,3-dimethylpyra zine (2,3-dmp), 2,5-dimethylpyrazine (2,5-dmp), 2,6-dimethylpyrazine (2,6-d mp), quinoxaline (qox), phenazine (phenz), 4,4'-bipyridine (4.4'-bpy) and t rans-4,4'-bipyridylethylene (dpe). Hydrothermal reactions of CuCN and KCN w ith the appropriate ligand yielded two general subclasses of materials: two -dimensional networks and three-dimensional frameworks. The 2-D phases incl ude [Cu-3(CN)(3)(pyr)] (1), [Cu-2(CN)(2)(etpyr)] (2), [Cu-2(CN)(2)(tMP)] (3 ), [Cu-2(CN)(2)(qox)] (4), [Cu-2(CN)(2)(phenz)] (5) and [Cu-7(CN)(7)(4,4'-b py)(2)] (6). The 3-D materials are represented by [Cu-3(CN)(3)(pyr)(2)] (7) , [Cu-2(CN)(2)(mpyr)] (8). [Cu-2(CN)(2)(2,3-dmp)] (9), [Cu-2(CN)(2)(2,5-dmp )] (10), [Cu-2(CN)(2)(2,6-dmp)] (11). [Cu-2(CN)(2)(4,4'-bpy)](12) and [Cu-2 (CN)(2)(dpe)] (13). The materials characteristically exhibit {Cu(CN)}(n) ch ains and/or {Cu-x(CN)(x)} rings as structural motifs. The detailed connecti vity between such substructures is influenced by the identity of the organo diimine ligand and the associated steric demands and spatial extension. The syntheses and structural characterization by X-ray diffraction of 1-13 are discussed in relation to the supramolecular chemistry of other copper cyan ide solid state materials.