From the reaction mixtures containing Cu(NO 3 ) 2 , Na[N(CN) 2 ], KPF 6 and 2,2¢-bipyridine (bpy) or 1,10-phenanthroline (phen) in 1:1:1:2 molar ratios, [Cu(bpy) 2 N(CN) 2 ][Cu(bpy) 2 (H 2 O)](PF 6 ) 3 (1b) and [Cu (phen) 2 N(CN) 2 ]PF 6 (1p) complexes were isolated. Measured i.r. spectra confirm the presence of all functional groups in both complexes and, moreover, they indicate monodentate coordination of dicyanamide through the cyano nitrogen atom in (1p). The structure of (1b) contains two crystallographically independent complex cations. In both, Cu is coordinated by two chelating bpy molecules, and either dicyanamide anion or water molecule fills the fifth position, completing the basal plane. The Cu II atoms in (1p) are coordinated by two chelating phen ligands and by one dicyanamide anion in the equatorial plane. Hexafluorophosphate anions in (1b) and (1p) remain uncoordinated. Besides the ionic forces in both structures, the structure of (1b) is stabilized by strong OAHÁ Á ÁF and OAHÁ Á ÁN hydrogen bonds and, moreover, both structures are stabilized by weak CAHÁ Á ÁF hydrogen bonds and possible p-p interactions between pyridine rings of bpy or phen molecules.

The title compound, [Cu(C(2)N(3))(C(12)H(8)N(2))(2)]ClO(4), represents a relatively rare class of compounds with dicyanamide coordinated in a monodentate manner. The structure is formed by the [Cu{N(CN)(2)}(phen)(2)](+) complex cation (phen is 1,10-phenanthroline) and an uncoordinated ClO(4)(-) anion. The Cu atom is five-coordinate, with a slightly distorted trigonal-bipyramidal environment. The dicyanamide ligand is coordinated through one nitrile N atom in the equatorial plane, at a distance of 2.033 (6) angstroms from the metal. The two axial Cu-N distances are similar [mean 1.999 (4) angstroms] and are substantially shorter than the remaining two equatorial Cu-N bonds [mean 2.087 (1) angstroms].

The ionic [Cu(C 2 N 3 )(C 10 H 8 N 2 ) 2 ](CF 3 SO 3 ) compound, which contains two crystallographic independent formula units, is formed by [Cu(bpy) 2 (dca)] + complex cations (bpy ¼ 2,2¢-bipyridine, dca ¼ dicyanamide) and uncoordinated CF 3 SO À 3 anions, which are in a staggered conformation. The shapes of coordination polyhedra around both copper atoms, which are fivefold coordinated by two bpy molecules and one dca ligand monodentately coordinated through a cyano N atom in the equatorial plane at a distance of 2.001(3) Å for the first and 1.988(4) Å for the second polyhedron, are distorted trigonal bipyramids. Besides the ionic forces the structure is stabilized by weak CAH Á Á Á O hydrogen bonds and possible p-p interactions between pyridine rings of bpy molecules. Along with the structural-spectral correlation we discuss the thermal decomposition of the title complex.

The title compound, [Cu(C2N3)(C3H10N2)2]ClO4, is made up of [Cu(tn)2{N(CN)2}]+ complex cations (tn is 1,3-diaminopropane) and ClO4- anions. The Cu(II) atom is coordinated by four N atoms of two equatorial tn ligands, with an average distance of 2.041 (7) A, and one nitrile N atom of the dicyanamide anion in an axial position, at a distance of 2.236 (3) A, in a manner approaching square-planar coordination geometry. The complex has C(s) symmetry, with the mirror plane lying through the central C atoms of both tn ligands and the dca ligand. The ClO4- anion might be considered as very weakly coordinated in the opposite axial position [Cu-O = 2.705 (3) A], thus completing the Cu(II) coordination to asymmetric elongated octahedral (4+1+1*). The Cu atom and the perchlorate anion both lie on mirror planes.