Gary L. Breneman

Crystal structure of a copper stabilized hydrate of di-2-pyridyl ketone

Abstract The addition of a yellow ethanolic solution of di-2-pyridyl ketone to a blue–green aqueous solution of copper(II) bromide produces an exothermic reaction and a brilliant purple solution. Brilliant purple single crystals were obtained from the solution by solvent evaporation and were subjected to a crystal structure determination. The structure of the isolated gem-diol compound stabilized by a transition metal contains two di(2-pyridyl)methanediol ligands bonded to the central copper atom in a distorted octahedral arrangement providing four nitrogen atoms at relatively short bond distances and two oxygen atoms at longer bond distances. In the solid state, both oxygen atoms on each of the gem-diol ligands are protonated.

Crystal and molecular structure and spectral properties of diisothiocyanato-(1,10-phenanthroline)copper(II)

Abstract Adding solid NH4SCN to a light blue solution which contains a pale green precipitate of Cu(phen)Cl2 produces a green solid that can be recrystallized to produce single crystals. The IR spectrum indicates that both ends of the thiocyanate ion bond to the copper. An X-ray structure determination verifies this conclusion. The structure of this complex has a four-coordinated distorted square-planar arrangement of nitrogen atoms with one nitrogen-bonded thiocyanate twisted above the plane described by copper and phen, and another thiocyanate twisted below the plane. The sulphur ends of the two thiocyanates form longer fifth and sixth bonds to copper atoms in adjacent molecules, forming a linear infinite chain of SCN− bridged copper atoms. The copper is thus six-coordinated with distorted tetragonal symmetry.

Crystal and molecular structure and spectral properties of bromosbis(1,10-phenanthroline)copper(II) perchlorate

Abstract The crystal and molecular structure of green [Cu(phen)2Br]ClO4, which contains a distinct Cu(phen)2Br+ cation and a separate perchlorate anion, was determined. The stereochemistry of the cation is a five-coordinate trigonal bipyramidal arrangement of four nitrogen atoms from the two 1,10-phenanthroline ligands and one bromide ion. The crystal and molecular symmetry has a two-fold axis parallel to the b axis through the copper, bromine and chlorine atoms. The copper to nitrogen distances are 2.091 A for the equatorial positions and 1.985 A for the axial positions. The bromide ion occupies the remaining equatorial position at a distance of 2.496 A from the copper. The Cu(phen)2Br+ cation has equatorial angles of 120° between one nitrogen on each phenanthroline and the bromide. This cation most closely resembles a trigonal bipyramidal arrangement when compared with the five-coordinate copper(II) complexes which have been reported.

Synthesis and characterization of dichloro[5,10,15,20-tetrakis(p-tolyl)porphyrinato]osmium(IV), a potential precursor to organometallic porphyrinato complexes of osmium

Abstract Dichloro[5,10,20-tetrakis(p-tolyl)porphyrinato]osmium(IV), Os(TTP)Cl2, was prepared by reaction of stannous(II) chloride dihydrate with dioxo[5,10,15,20-tetrakis(p-tolyl)porphyrinato]osmium(VI), Os(TTP)O2. The compound was characterized by 1H NMR, IR, and UV-Visible spectroscopy and by X-ray crystallography. The compound has a trans-dichloro configuration with octahedral Os(IV). The short OsCl bond distances of 2.294(2) A, magnetic moment of 1.63 BM, and isotropic shifts in the 1H NMR spectrum are consistent with π-donation from the halide.

Second crystal form of dinitrito(1,10‐phenanthroline)copper(II)

The crystal structure of a second form of green [Cu(NO2)2(phen)], where phen is 1,10-phenanthroline (C12H8N2), containing six-coordinate copper(II) with a distorted tetragonal [CuIIN2O4] core is reported. The first form had a crystal symmetry of C2/c [Breneman et al. (1999). Acta Cryst. C55, IUC9900158], while the form reported here is Pbcn. The nitrito ligands are bonded to the central copper through both O atoms, with short Cu—O bond distances of 1.987 (3) A and longer Cu—O bond distances of 2.410 (4) A. Both nitrito groups are significantly displaced from the plane defined by the 1,10-phenanthroline and the square-planar arrangement of the ligands around the CuII atom.

Structure of bis(2-chloroethyl)ammonium hexachlorostannate

[(ClCH2CH2)2NH2]2SnCl6, M(r) = 617.48, monoclinic, C2/c, a = 15.67 (2), b = 13.54 (2), c = 13.24 (2) A, beta = 127.9 (2) degrees, V = 2217 A3, Z = 4, D chi = 1.85 g cm-3, lambda(Mo K alpha) = 0.71073 A, mu = 23.70 cm-1, F(000) = 1208, T = 295 K, R = 0.058, wR = 0.071 for 1231 unique reflections. The structure consists of discrete (ClCH2CH2)2NH2+ cations and octahedral SnCl6(2-) anions with the Sn sitting on the twofold axis.