EPR study of solid solutions of [Cr(NH3)5Cl]x[Rh(NH3)5Cl]1?x[PdCl4]·nH2O and [Cr(NH3)5Cl]x[Rh(NH3)5Cl]1?x[PtCl4] compounds

In order to determine the features of the structure of double complex salts (DCSs) of [Cr(NH₃)₅Cl]×[MCl₄]·nH₂O, where M = Pd, Pt, n = 0, 1, the DCS solid solutions of palladium and platinum with isostructural DCSs containing the chloropentaammine rhodium cation, [Cr(NH₃)₅Cl] _x [Rh(NH₃)₅Cl]_1−x [MCl₄]·nH₂O, where x = 0.01–0.2, are synthesized and studied by the EPR method. DCSs with the isostructural chloropentaammine rhodium cation are used as a diluter for magneto concentrated systems. It is shown that DCS of platinum and anhydrous DCS of palladium have the identical environment of chromium ions. The EPR spectra of chromium ions for these compounds are described by the following spin Hamiltonian parameters: S = 3/2, g _xx = 1.987, g _yy = 1.987, g _zz = 1.985, D = 1660 Gs, E = 235 Gs. For the palladium complex containing crystalline water, the EPR spectra of chromium ions are described by the parameters: S = 3/2, g _xx = 1.984, g _yy = 1.984, g _zz = 1.984, D = 1060 Gs, E = 350 Gs. A decrease in the crystal field parameters for the aqueous palladium complex is caused by a redistribution of the electron density to the oxygen atom in the second sphere of the chromium ion environment.     

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.     

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 X-ray diffraction study of complex oxides of the Zn2 ? x(ZraSnb)1 ? xFe2xO4 composition

A multicomponent system of complex refractory oxides of the composition Zn_{2 − x} (Zr _a Sn _b )_{1 − x} Fe_2x O₄ (a + b = 1; a: b = 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 2: 1, 3: 1, 4: 1; x = 0−1.0; Δx = 0.05) was studied by X-ray diffraction. The samples were prepared from oxides of appropriate metals by low-temperature plasma synthesis (hydrogen-oxygen flame). Two phases with wide homogeneity ranges were identified: α phase crystallized in the crystal system of inverse cubic spinel and β phase with the structure of tetragonal spinel. The phase boundaries were found. Structural data are presented for about 100 solid solutions.     

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⁻.     

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.     

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.     

[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.     

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.     

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).     

配合物(BenzMeIm)2[PtCl4]的合成与表征

通过离子液体氯化1-苄基-3-甲基咪唑（BenzMeIm-Cl）与PtCl₂的反应,合成了配合物（BenzMeIm）₂[PtCl₄],并用元素分析、红外光谱、紫外-可见光谱、¹H NMR、¹³C NMR和单晶X射线衍射对其进行了表征。单晶X射线分析表明,配合物结构属于P2₁/c空间群,晶胞参数和结构解析参数为：a=0.981 80（5）nm,b=0.861 47（3）nm,c=0.144 332（7）nm,β=92.480（2）°,V=121.96（1）nm³,R₁=0.014 4,wR₂=0.038 8。     

Ca2-3xLa8+2x□x(SiO4)6O2的合成及其导电性能的研究

The silicate oxyapatites Ca_2-3xLa_8+2x□_x(SiO₄)₆O₂(x=0, 0.17, 0.33, 0.50, 0.67) was synthesized via a sol-gel method at low temperature. The apatite phases have been characterised by X-ray diffraction (XRD), conducting properties was studied by electrical chemistry impedance spectroscopy (EIS). The conductivity of La_9.33□_0.67(SiO₄)₆O₂ is 1.58×10^-3 S·cm^-1 at 700 ℃, it is higher about 4 270 times than that of Ca₂La₈(SiO₄)₆O₂, the activation energy is decreasing from 1.37 eV to 0.84 eV. With cation vacancies increasing,the conducting mechanism is gradually translation from a direct linear pathway free oxygen ion conduction to a curve pathway interstitial oxygen ion conduction. The electrical conductivities is almost independent of the oxygen partial pressure, this suggests that the oxyapatites exhibited almost pure O^2- ion conduction over a wide range of oxygen partial pressure.     

配合物(BenzMeIm)2[PtCl4]的合成与表征

通过离子液体氯化1-苄基-3-甲基咪唑（BenzMeIm-Cl）与PtCl₂的反应,合成了配合物（BenzMeIm）₂[PtCl₄],并用元素分析、红外光谱、紫外-可见光谱、¹H NMR、¹³C NMR和单晶X射线衍射对其进行了表征。单晶X射线分析表明,配合物结构属于P2₁/c空间群,晶胞参数和结构解析参数为：a=0.981 80（5）nm,b=0.861 47（3）nm,c=0.144 332（7）nm,β=92.480（2）°,V=121.96（1）nm³,R₁=0.014 4,wR₂=0.038 8。     

Synthesis and study of the variable-composition phase Na1?xCo1?xFe1+x(MoO4)3, 0 ≤ x ≤ 0.4, with nasicon structure

The synthesis conditions for variable-composition phase Na_1−x Co_1−x Fe_1+x (MoO₄)₃, 0 ≤ x ≤ 0.4, crystallizing in the nasicon structure type (R $ \bar 3 $ \bar 3 c) were examined. For this phase, the crystallographic parameters were calculated, vibrational spectra were interpreted, and temperature dependence of electrical conductivity, dielectric constant, and dielectric loss tangent were examined.     

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.     

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.     

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.     

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.     

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.