Coordination polymers of copper(I) halides.

A total of 21 complexes of CuX (X = Cl, Br, I) with bridging ligand (B = 4,4'-dipyridyl (Bpy), pyrazine (Pyz), quinoxaline (Quin), phenazine (Phz), 1,4-diazabicyclo[2.2.2]octane (DABCO), and hexamethylenetetramine (HMTA)) have been synthesized. The products show two stoichiometries: [CuXB] (type 1) and [(CuX)2B] (type 2). Both types can be obtained for B = Bpy, depending on the conditions of preparation. In these cases, the type 2 stoichiometry is the kinetic product. Type 2 complexes only are found for B = Pyz (X = I), Quin, Phz, DABCO, and HMTA. Type 1 complexes form for Pyz (X = Cl, Br). Thermogravimetic analyses of the complexes reveal the general decomposition trend: 1 --> 2 --> [(CuX)2B(1/2)] --> CuX. The X-ray crystal structure of [CuBr(Pyz)] (type 1) features copper atoms bridged by Br and Pyz, forming 2D sheets of fused rectangular Cu4Br2(Pyz)2 units. The X-ray structure of [(CuI)2(Quin)] (type 2) shows 2D layers composed of [Cu2I2]infinity "stair step" chains which are cross-linked by Quin ligands. A total of 16 complexes of CuXL (L = P(OPh)3) with bridging ligand (B = those above and 1,4-dimethylpiperazine (DMP)) have also been prepared. All of these products, except those of HMTA, are of type 3 formulation, [(CuXL)2B]. The HMTA products have the formula [CuX(HMTA)], type 4. Thermal decomposition of the type 3 and 4 complexes occurs with initial loss of B, L, or both. The X-ray structures of [(CuBrL)2(Bpy)] and [(CuBrL)2(Pyz)] (type 3) reveal 1D chains formed from rhomboidal (LCu)2Br2 units linked by the B ligand. The type 4 structure of [CuBrL(HMTA)] is shown by X-ray to be a simple halide-bridged dimer.

Cubane tetrameric complexes of copper(I) chloride and bromide with triphenyl phosphite.

The crystal structures of tetra-mu 3-chloro-tetrakis[(triphenyl phosphite-P)copper(I)], [Cu4Cl4(C18H15O3P)4], and tetra-mu 3-bromo-tetrakis [(triphenyl phosphite-P)-copper(I)], [Cu4Br4(C18H15O3P)4], are described. Both have distorted 'cubane' Cu4X4 cores. Distortion of the cubane structure is reflected in X-Cu-X angles > 90 degrees and Cu-X-Cu angles < 90 degrees, and is more pronounced in the bromide complex.

Azidotetrakis(trimethylphosphine)nickel(II) tetrafluoroborate.

The title complex, [Ni(N3)(C3H9P)4]BF4, is a nearly perfect trigonal bipyramid with the azide group at an apical position. The metal-azide bond angle, Ni1--N1--N2, of 138.6(5) degrees is the largest observed for a terminal azide ligand.