The crystal structure determinations of Lu−b3−sS−b4−s, nonstoichiometric Nb−b1−s−ḅ06−sS−b2−s, and three Group VIII coordination complexes

Powell, Douglas
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The crystal structures of five selected inorganic compounds have been determined from single crystal x-ray measurements. Each of these materials was found to have interesting and novel structural features. A brief description of the structural results of each compound is discussed below;Metallic Lu(,3)S(,4) was found to crystallize in the orthorhombic space group F(,ddd) with a = 10.747(3), b = 22.813(6), and c = 7.602(2)(ANGSTROM). The lattice is a supercell of the rock-salt structure type, similar to LuS which has a = 5.43(ANGSTROM). The metal occupancies form sheared population waves which are normal to the (066) orthorhombic lattice planes. Several crystals exhibited a disordering of the orthorhombic lattice over the cubic sublattice;The 3-R form of Nb(,1.06)S(,2) crystallizes in the space group R(,3m) with hexagonal lattice parameters a = 3.3285(4) and c = 17.910(4)(ANGSTROM). The principal niobium sites, which are 0.97(1) occupied, are surrounded by trigonal prisms of sulfurs; the additional 0.09(1) niobium occupies distorted octahedral sites in the van der Waals layers. The octahedral distortions are due to repulsion of the additional niobium by metal in the principal sites;The compound bis((delta)-camphorquinonedioximato)nickel(II), Ni((delta)-HCQD)(,2), crystallizes in the orthorhombic space group P(,2(,1)2(,1)2(,1)) with a = 13.175(1), b = 13.652(2), and c = 12.031(3)(ANGSTROM). The ligands bond to the metal in a trans square-planar configuration via nitrogen and oxygen donor atoms. Absorption maxima in the infrared spectra at 1560 cm('-1) and 1690 cm('-1) are believed to be characteristic of vic-dioxime complexes which are N,O coordinated. There are no metal-metal or intermolecular hydrogen bonds in this structure;The hexanuclear cluster complex Ni((delta)-HCQD)(,2) (.) Ag(,3) (.) 2 1/2 CHCl(,3) crystallizes in the orthorhombic space group P(,2(,1)2(,1)2(,1)) with a = 15.990(5), b = 38.44(1), and c = 13.437(5)(ANGSTROM). This complex is prepared by the reaction of Ni((delta)-HCQD)(,2) with silver nitrate. Three Ni((delta)-HCQD)(,2)('-) groups are bonded to a linear backbone of three silver atoms. The ligands in the Ni((delta)-HCQD)(,2)('-) groups have changed from trans to cis configurations around each nickel. The solvent groups are disordered over three sites;The compound cis-dichlorobis(methyldiphenylphosphinite)-palladium(II) crystallizes in the monoclinic space group P(,2(,1)/n) with a = 12.539(6), b = 13.741(4), c = 15.147(4)(ANGSTROM), and (beta) = 94.6(5)(DEGREES). The phosphinite and chloride ligands coordinate to the metal in a cis square-planar configuration. The opening of the Cl-Pd-Cl angle 92.3(2)(DEGREES) is believed due to weakened Pd-Cl bonds and intramolecular hydrogen bond attractions between the chlorines and the phosphinite ligands;*DOE Report IS-T-911. This work was performed under Contract W-7405-eng-82 with the Department of Energy.