S. A. Gromilov

New polymeric structure of rhenium octahedral chalcocyanide complex: Ln3+-derived network with one-dimensional channels

Abstract A novel cyanobridged coordination polymeric complex with octahedral rhenium cyanocluster anion [Re6(μ3−Se)8(CN)6]4− and Nd3+ cation has been synthesised and structurally characterised. Its solid-state structure contains a channel-type polymeric network built from cluster anions and Nd3+ through ReCNNdNCRe interactions. For compound (H3O){Nd(DMF)3(H2O)3}[Re6Se8(CN)6], space group R3c, unit cell parameters are: a=32.514(5); c=25.255(5) A, V=23122(7) A3, Rf=0.0762. A pair of isomorphic complexes has been obtained with Ln=Pr3+,Ho3+.

Synthesis and Structure of Binary Complexes of Platinum Group Metals — Precursors of Metallic Materials

This paper reviews the results of structural studies of binary complexes whose cationic part contains cobalt, rhodium, iridium, ruthenium, and chromium chloropentammne. The structure of these compounds is discussed in the light of the design of new multicomponent precursor compounds. Data are given on the chemical and phase compositions of the polymetallic powders resulting from the thermal decomposition of the compounds studied.

The preparation, structures and thermal properties of [Men3][Cd(S2CNEt2)3]2 [M = zinc(II), cadmium(II)] complexes

Abstract New complexes of the general formula [MEn3][CdL3]2 [M = Cd (I), Zn (II), En = NH2CH2CH2NH2, L = Et2NCS2−) have been prepared and their crystal structures have been determined. Complexes I and II are isostructural. In the [MEn3]2+ cation, the metal atom is six-coordinated by the nitrogen atoms of three ethylenediamines forming a distorted octahedron, while in the [CdL3]− anion the metal atom is six-coordinated by the sulphur atoms of three bidentate L ligands forming a distorted trigonal prism. The thermal behaviour investigation of complexes I and II has shown that the final products of their thermolysis are CdSwur and Zn0.25Cd0.75Swur, respectively.

Synthesis and crystal structure of trans-nitrosoaquatetraammineruthenium(II) sulphate hydrosulphate, [Ru(NO)(NH3)4(H2O)](SO4)(HSO4)

Abstract The reaction between [RuNO(NH 3 ) 4 OH]Cl 2 and an excess of 2 M H 2 SO 4 leads to the protonation of the starting complex and crystallisation of the title complex with sulphate and hydrosulphate anions. The crystal structure of the product has been determined. The linear nitroso group and water molecule are coordinated in trans positions.

Syntheses of [Rh(NH3)5Cl][MCl6] (M = Re, Os, Ir) and Investigation of Their Thermolysis Products. Crystal Structure of [Rh(NH3)5Cl][OsCl6]

Binary complex salts [Rh(NH3)5Cl][MCl6], where M = Re, Os, Ir, have been synthesized and characterized. X-ray diffraction analysis indicated that the salts are isostructural. According to X-ray phase analysis, the products of their thermolysis in hydrogen are monophase stoichiometric nonequilibrium solid solutions Rh0.5M0.5 (M = Re, Os, Ir). The molecular and crystal structures of [Rh(NH3)5Cl][OsCl6] were determined in an X-ray structural analysis.

Crystal structures of [Pd(En)2](ReO4)2, [Pd(En)2](NO3)2, and [PdL2](ReO4)2 (L: N,N′-diiso-propylideneethane-1,2-diamine)

At T = 150 K, the crystal structures of [Pd(En)2](ReO4)2, [Pd(En)2](NO3)2, and [PdL2](ReO4)2 (L is N,N′-diisopropylideneethane-1,2-diamine) are studied. Crystal chemical analysis is performed, and the main factors affecting the packing of fragments in these structures are determined.

Tetrabutylammonium Salts of Ruthenium(II) Nitroso Complexes

The paper describes synthesis of (n‐Bu4N)2[RuNOCl5](I), (n‐Bu4N)2[RuNOCl4OH](II), (n‐Bu4N)2×[RuNOCl4OH]·6H2O (III), and (n‐Bu4N)2[RuNOCl5]· 2(n‐Bu4N)2[RuNOCl4(H2O)]·2H2O (IV). The complexes were studied by IR spectroscopy and powder X‐ray and crystal X‐ray analyses. The structures are built up of [RuNOCl5]2- (I, IV), [RuNOCl4OH]2- (II, III), and [RuNOCl4(H2O)]- (IV) complex anions, (n‐Bu4N)+ cations, and crystal water molecules (III, IV). The substances are moderately soluble in water; highly soluble in polar organic solvents, such as acetone, ethanol, chloroform, methylene chloride; and almost insoluble in carbon tetrachloride and toluene. Under storage in light, the compounds decompose from the surface; in darkness I and II are stable, whereas III and IV can lose part of the crystal water.

Synthesis and crystal structure of scandium(III) and cadmium(II) thiocyanato complexes with dimethylsulfoxide

Abstract Two novel complex compounds, molecular fac-[Sc(NCS)3(DMSO)3] and polymeric chain [Cd(NCS)4/2(DMSO)2]∞ (DMSO = dimethylsulfoxide), were synthesized and structurally characterized. In both complexes, the metal atoms have octahedral coordination with the NCS− ion serving two different functions: as a terminal ion with the coordination via N in Sc complex and as a bridge ligand with the coordination via N and S in the case of Cd compound, respectively. The DMSO ligands are coordinated by oxygen atoms.

Synthesis and crystal structure of Na2[RuNOCl5] · 6H2O

A procedure for the synthesis of Na2[RuNOCl5]·6H2O is described. The complex was studied by IR spectroscopy and by thermal, X-ray phase, and X-ray diffraction analyses. Crystal data: a = 26.740(7), b = 31.581(7), c= 6.918(3) Å, V = 5842(3) Å3 space group Fdd2. Z = 16, dcalc= 2.103, dexp = 2.112 g/cm3. The structure consists of [RuNOCl5]2− complex cations, Na+ cations, and crystallization water molecules. The compound is stable in conditions of high humidity of atmosphere but irreversibly loses up to four water molecules when stored in dry atmosphere. Removal of two water molecules is accompanied by crystal decay and changes in the crystal structure. Heating the substance above 100°C leads to a hygroscopic anhydrous complex Na2[RuNOCl5], which is stable below t = 375°C.

Crystal and molecular structure oftrans-bis-(1,1,1-trifluoro-5-methoxy-5-methyl-2,4-hexanedionato) copper(II)

A combined X-ray diffraction study of the single crystals (Enraf-Nonius CAD-4 automatic diffractometer, MoKα radiation, graphite monochromator) and polycrystals (DRON-UM1, CuKα radiation, Ni filter) of a new volatile complex of Cu(II) obtained from fluorinated alkoxy-Β-diketone, CF3-CO-CH2-CO-C(CH3)2OCH3, is reported. The compound has a molecular structure; the crystals consist of trans-bis(1,1,1-trifluoro-5-methoxy-5-methyl-2,4-hexanedionato)copper(II) complexes. The structure was refined anisotropically for 2314 independent reflections with I > 2Σ(I) to R = 0.069. Crystal data: a = 24.469(3), c = 10.581(2) å, V = 5486.4 å3, space group R3, Z = 9, dcalc = 1.17 g/cm3. The complexes are packed to form through channels ≈5 å in diameter along the c axis, with terminal fluorine atoms facing the channels. The crystal-chemical data of the compound are compared with those of the nonfluorinated analog, trans-bis(2-methoxy-2,6,6-trimethylheptane-3,5-dionato)copper(II). The introduction of CF3 groups into alkoxy-Β-diketone considerably decreases the sublimation temperature of the complex. The geometrical characteristics of chelate nodes in the complexes are almost equal: the Cu-0 distances are 1.92 å and the O-Cu-0 bond angles 92.1‡ (average). In both cases, the square planar environment of the Cu atom is completed to bipyramidal by interactions with the oxygen atoms of the methoxy groups of the neighboring molecules, with Cu...O distances being 2.8 å.