Structure and thermal properties of [Ir(NH3)5Cl]x[Rh(NH3)5Cl]1?xMO4 (x = 0.5, 1; M = Mo, W)

Complex salts [Ir(NH₃)₅Cl]x[Rh(NH₃)₅Cl]_1−x MO₄ (x = 0.5, 1; M = Mo, W) are synthesized and their thermal properties are studied. The crystal structures are determined for [Ir(NH₃)₅Cl]WO₄ and [Ir(NH₃)₅Cl]MoO₄. In the structures, the ions are linked by N-H...O hydrogen bonds, the shortest ones being 2.868(2)–3.422(2) ?. and 2.860(4)–3.434(3) ?. respectively. The thermal properties of the complex salts are studied in the hydrogen atmosphere and in hydrogen-helium mixtures. It is demonstrated that the final products are the mixtures of nanocrystalline powders of Ir and binary or ternary solid solutions with the hcp lattice.     

X-ray study of the thermolysis products of (NH4)2[OsCl6]x[PtCl6]1?x

Thermolysis of the complex salts (NH₄)₂[OsCl₆] _x [PtCl₆]_1−x (x = 0.25−0.9) formed nanocrystalline Os _x Pt_1−x phases. Pseudomorphism has been found: the habit of the single crystals of the starting salts is preserved during thermolysis, and the ∼10–20 nm metal particles are agglomerated into octahedral structures sized 5–10 μm.     

Double complex salts [Pd(NH3)4]3[Rh(NO2)6]2, [Pd(NH3)4]3[Rh(NO2)6]2·H2O as promising precursors to prepare Pd-Rh nanoalloys

Two new double complex salts [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂ (I) and [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂·H₂O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) ?, V = 6767.4 ?³, F-43c space group, Z = 8, d _x = 2.548 g/cm³; II: a = 21.160(6) ?, b = 8.085(7) ?, c = 21.363(4) ?, β = 91.71(4)°, V = 3661.1(6) ?³, P2₁/c space group, d _x = 2.357 g/cm³. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd_0.59Rh_0.41 (Fm-3m space group, a = 3.856(2) ?, crystallite size of 8–11 nm).     

Structure of complex salts [Co(NH3)6][Rh(NO2)6] and [Co(NH3)6][(NO2)3Rh(μ-NO2)1+x(μ-OH)2?xRh(NO2)3]·(2-x)(H2O), x = 0.17

The structures of two salts [Co(NH₃)₆][Rh(NO₂)₆] (I) and [Co(NH₃)₆][(NO₂)₃Rh(μ-NO₂)_1+x (μ-OH)_2−x Rh(NO₂)₃]·(2−x)(H₂O), x = 0.17 (II) are solved. Single crystals of the salts are obtained by the counter diffusion method through the gel of aqueous solutions of [Co(NH₃)₆]Cl₃ and Na₃[Rh(NO₂)₆]. The structure of [Co(NH₃)₆][Rh(NO₂)₆] is consistent with the diffraction data for a polycrystalline sample of poorly soluble fine salt formed in the exchange reaction between aqueous solutions of [Co(NH₃)₆]Cl₃ and Na₃[Rh(NO₂)₆]. The structure of [Co(NH₃)₆][(NO₂)₃Rh(μ-NO₂)_1+x (μ-OH)_2−x Rh(NO₂)₃]·(2−x)(H₂O), x = 0.17 exhibits the stabilizing effect of a large cation in the formation of novel, unknown previously coordination ions: [(NO₂)₃Rh(μ-NO₂)(μ-OH)₂Rh(NO₂)₃]³⁻ and [(NO₂)₃Rh(μ-NO₂)₂(μ-OH)Rh(NO₂)₃]³⁻.     

Double complex salts with [Ru(NH3)5Cl]2+ cation and [OsCl6]2? anion: Synthesis and properties. Crystal structure of [Ru(NH3)5Cl]2[OsCl6]Cl2

Double complex salts [Ru(NH₃)₅Cl][OsCl₆] and [Ru(NH₃)₅Cl]₂[OsCl₆]Cl₂ were prepared and characterized. An X-ray diffraction study showed that [Ru(NH₃)₅Cl][OsCl₆] is isostructural to the previously synthesized [Rh(NH₃)₅Cl][OsCl₆]. The structure of [Ru(NH₃)₅Cl]₂[OsCl₆]Cl₂ was solved by X-ray diffraction (a = 11.1849(8) ?, b = 7.9528(6) ?, c = 13.4122(9) ?; β = 99.765(2)°; V= 1175.75 ?³; space group C2/m; Z = 2). Thermolysis of the compounds under hydrogen and helium was studied. According to X-ray diffraction, nanosized metallic powders of the corresponding alloys are formed as the final products of thermolysis. The compositions of the obtained solid solutions are consistent with the phase diagram of the Ru-Os system.     

Crystal structure of [Pd(NH3)4]3[Ir(NO2)6]2·H2O

A single crystal of [Pd(NH₃)₄]₃[Ir(NO₂)₆]₂·H₂O double complex salt is studied by X-ray diffraction. Crystallographic characteristics are as follows: a = 21.0335(5) ?, b = 8.0592(2) ?, c = 21.3452(5) ?, β = 91.254(1)°, V = 3617.43(15) ?³, P2₁/c space group, Z = 4, d _x = 2.714 g/cm³. Single-layer pseudohexagonal packing of complex anions is determined along the [−1 0 1] direction in the structure. Complex cations and crystallization water molecules are located between the mentioned layers.     

Crystal structure of [Pt(NH3)5Cl](PO4) · 2H2O

Polycrystals of [Pt(NH₃)₅Cl](PO₄)·2H₂O complex salt are analyzed using single crystal XRD (STADI-P autodiffractometer, CuKα₁-radiation, position sensitive detector). Crystallographic characteristics are as follows: a = 9.2447(2) ?, b = 7.3122(1) ?, c = 9.2005(1) ?, β= 109.938(1)°, P2₁/m space group, V = 584.67(2) ?³.     

Pseudohexagonal motif of the arrangement of compex anions in the structure of [Ru(NH3)5Cl]2[Re6S8(CN)6]·3H2O

The [Ru(NH₃)₅Cl]₂[Re₆S₈(CN)₆]·3H₂O salt was obtained; its crystal structure was analyzed: a = 10.7713(9) Å, b = 13.9602(11) Å, c = 14.7956(11) Å, α = 91.961(3)°, β = 109.985(3)°, γ = 110.030(3)°, V = 1935.3(3) ų, space group P1ˉ, Z = 2, d _calc = 3.441 g/cm³. In the cluster anion, the Re-Re distances lie in the range from 2.594 Å to 2.612 Å. For two crystallographically independent complex cations, Ru-N_av is 2.105 Å, and Ru-Cl_av 2.329 Å. A pseudohexagonal motif of the structure was found. Original Russian Text Copyright ? 2008 by K. V. Yusenko, I. A. Baidina, E. A. Shusharina, and S. A. Gromilov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 1, pp. 178–181, January–February, 2008.     

Specifics of pyrohydrolytic and solid-phase syntheses of solid solutions in the (MgGa2O4)x(MgFe2O4)1 ? x system

This work demonstrates the possibility of preparing solid solutions in the (MgGa₂O₄) _x (MgFe₂O₄)_{1 − x} system by pyrohydrolytic and solid-phase methods. It is shown that the products obtained have different specific surface areas depending on the ratio between metal nitrates and citric acid. The composition dependence of the unit cell parameter deviates considerably from the Vegard’s rule. The compounds obtained are found to be stable up to 300°C, which makes them candidate materials for electronics.     

Crystal structure of a tetrahedral cluster complex [Zn2(NH3)6(μ-OH)][Zn(NH3)4]0.5[Re4Te4(CN)12]·5H2O

A cluster complex of the composition [Zn₂(NH₃)₆(μ-OH)][Zn(NH₃)₄]_0.5[Re₄Te₄(CN)₁₂]·5H₂O is obtained by the interaction of an aqueous solution of K₄[Re₄Te₄(CN)₁₂]·5H₂O with an aqueous ammonia solution of ZnCl₂. The compound crystallizes in the C2/m (12) monoclinic space group with unit cell parameters a = 23.233(2) ?, b = 14.5906(16) ?, c = 14.3825(15) ?, β = 125.169(1)°, V = 3985.5(7) ?³, Z = 4, d _x = 3.290 g/cm³. The structure is built from cluster [Re₄Te₄(CN)₁₂]⁴⁻ anions and complex [Zn₂(NH₃)₆(μ-OH)]³⁺ and [Zn(NH₃)₄]²⁺ cations; the latter is disordered over two positions.     

Cationic mobility in Li3?2xNbxFe2?x(PO4)3 complex phosphates

Synthesis and ionic conductivity of Li_3−2x Nb _x Fe_2−x (PO₄)₃ complex phosphates were studied by X-ray powder diffraction and impedance spectroscopy. These phosphates are formed only at 900–1000°C. Variations in their thermal expansivity and unit cell parameters induced by aliovalent doping were characterized. The conductivity of these materials increases monotonically in the series Li_0.5Nb_1.25Fe_0.75(PO₄)₃-LiNbFe(PO₄)₃ and Li_1.2Nb_0.9Fe_1.1(PO₄)₃-Li₃Fe₂(PO₄)₃, which is explained by consecutive occupation of the Li(1) and Li(2) positions in their structures. Original Russian Text ? A.R. Shaikhlislamova, I.A. Stenina, A.B. Yaroslavtsev, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 12, pp. 1957–1962.     

Mixed-ligand complexes [Cd(DMSO)5(NCS)][Cr(NH3)2(NCS)4] · 3DMSO and [Mn(DMSO)4(H2O)2][Cr(NH3)2(NCS)4]2 · 6DMSO · 2H2O: Syntheses and crystal structures

New mixed-ligand coordination compounds[Cd(DMSO)₅(NCS)][Cr(NH₃)₂(NCS)₄] · 3DMSO (I) and [Mn(DMSO)₄(H₂O)₂][Cr(NH₃)₂(NCS)₄]₂ · 6DMSO · 2H₂O (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction analysis. The crystals of compound I are monoclinic, a = 14.5275(7), b = 23.1692(11), c = 14.6969(6) ?, β = 97.057(2)°, V = 4909.4(4) ?³, space group P2₁/c, Z = 4, ρ_calcd = 1.507 g/cm³, R = 0.0556. The crystals of compound II are triclinic, a = 11.7784(3), b = 12.1760(3), c = 13.1922(2) ?, α = 85.5420(10)°, β = 87.9000(10)°, γ = 70.3680(10)°, V = 1776.46(7) ?³, space group P , Z = 1, ρ_calcd = 1.444 g/cm³, R = 0.0350. Original Russian Text ? E.A. Gerasimova, T.V. Utkina, E.V. Peresypkina, A.V. Virovets, T.G. Cherkasova, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 5, pp. 751–755.     

A study of the structure of (HfO2)x(Al2O3)1?x/Si films by X-ray photoelectron spectroscopy

By X-ray photoelectron spectroscopy (XPS), using the technique of layer-by-layer analysis, the films of (HfO₂) _x (Al₂O₃)_1−x solid solutions synthesized by chemical vapor deposition are studied. The possibility to determine the structure of solid binary solutions based on the analysis of the XPS spectra is demonstrated.     

Synthesis and study of the properties of K2Y1 ? x ? yEuxTby(MoO4)(PO4) and K2Y1 ? x ? yEuxTby(MoO4)(PO4)1?δ(VO4)δ solid solutions

Al synthesized samples are isostructural and crystallize in the orthorhombic symmetry system, space group Ibca. Particles of the final product of ∼200 nm in size have been obtained. The introduction of the vanadate anion into the matrix composition leads to the lowering of the symmetry of the Eu³⁺ environment and to the rise of the defect luminescence at 450–550 nm because of the unit cell distortion. The luminescence of defects in terbium-europium-containing samples is determined by the sample surface area, which decreases on annealing. The τ, W ₀ and γ parameters of the luminescence kinetics of the samples have been determined.     

Structure and luminescence of [Tb0.5(C6NO2H5)3(H2O)2]2n·(H3O)4n(ZnCl5)n(ZnCl4)2n

A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex [Tb_0.5(C₆NO₂H₅)₃(H₂O)₂]_2n ·(H₃O)_4n (ZnCl₅) _n (ZnCl₄)_2n (1) is synthesized. It has a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that it displays interesting emissions in the violet, blue, green, and yellow regions.     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

First example of ruthenium nitroso monoammine complex. Crystal structure of [Ru(NO)(NH3)3(H2O)Cl] × [Ru(no)(NH3)3(OH)Cl][Ru(NO)(NH3)Cl4]2Cl·2H2O

The structure of the interaction products of (NH₄)₂[Ru(NO)Cl₅] solution with ammonium acetate on heating is studied. The crystal structure of the [Ru(NO)(NH₃)₃(H₂O)Cl][Ru(NO)(NH₃)₃(OH)Cl] × [Ru(NO)(NH₃)Cl₄]₂Cl-2H₂O compound (compound I) containing a previously unknown anion of the nitrosomonoammine series is determined: Cc space group; a = 33.530(7) ?, b = 8.202(2) ?, c = 11.844(2) ?; β= 101.54(3)°.     

Cation mobility in modified Li1 ? xTi2 ? xNbx(PO4)3 lithium titanium NASICON phosphates

Li_{1 − x} Ti_{2 − x} Nb _x (PO₄)₃ NASICON materials are prepared and studied by X-ray diffraction, ⁷Li and ³¹P NMR spectroscopy, and impedance spectroscopy. Vacancy mobility in Li_{1 − x} Ti_{2 − x} Nb _x (PO₄)₃ is lower than interstitial lithium mobility. Nb⁵⁺ cations with low doping levels increase cation mobility in LiTi₂(PO₄)₃. Original Russian Text ? I.Yu. Pinus, I.A. Stenina, A.I. Rebrov, N.A. Zhuravlev, A.B. Yaroslavtsev, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 8, pp. 1240–1244.     

Crystal structures of La1 ? xSr2 + x(GeO4)(V1 ? xMoxO4) (x= 0?0.4) solid solutions

The phase compositions of theLaVO₄-SrMoO₄(1) and Sr₂GeO₄-SrMoO₄ (2) binary systems, which bound the Sr₂GeO₄-LaVO₄-SrMoO₄ (3) ternary system, and the LaSr₂(VO₄)(GeO₄)-Sr₂GeO₄+SrMoO₄ section (4) of system 3 are studied at subsolidus temperatures. Systems 1 and 2 consist of a mixture of the initial compounds, and the La_{1 − x} Sr_{2 + x} (GeO₄)(V_{1 − x} Mo _x O₄) (where 0 ≤ x ≤ 0.4) region of substitutional solid solutions with a palmierite structure is formed in system 3. The unit cell parameters of the solid solutions are determined. The distribution of the lanthanum and strontium cations over two positions of the cationic sublattice is described. Original Russian Text ? V.D. Zhuravlev, V.G. Zubkov, A.P. Tyutyunnik, Yu.A. Velikodnyi, N.D. Koryakin, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 1, pp. 135–137.     

New supramolecular adducts of chloroaquacomplexes [M3(μ3-S)S3?xSexCly(H2O)9?y](4?y)+ (M = Mo, W) with cucurbit[6]uril

New supramolecular adducts of cucurbit[6]uril with triangular cluster chloroaquacomplexes of Mo and W with mixed sulfido-selenido bridging ligands, {[W₃S₃Se(H₂O)₇Cl₂]₂(C₃₆H₃₆N₂₄O₁₂)}Cl₂·15H₂O (1), {[W₃S_1.5Se_2.5Cl_1.5(H₂O)_7.5]₂(C₃₆H₃₆N₂₄O₁₂)}Cl₅·18.5H₂O (2), and {[Mo₃SSe₃(H₂O)_7.5Cl_1.5]₂× (C₃₆H₃₆N₂₄O₁₂)}C_l5·11H₂O (3) are obtained treating the mixture of products in Mo-S-Se-Br and W-S-Se-Br systems, isolated, and structurally characterized. In all compounds, the supramolecular structure is based on hydrogen bonded associates of cucurbit[6]uril molecule with two cluster cations.