Crystal structure of the pyrovanadate K4V2O7

The crystal structure of anhydrous K₄V₂O₇ (I) is determined by powder X-ray diffraction. The compound crystallizes in the monoclinic system (a = 10.222(1) Å, b = 6.2309(8) Å, c = 7.282(1) Å, β = 101.31(1)°, space group C2/m, Z = 2). The structure contains layers of isolated V₂O₇ pyrovanadate groups separated by layers of potassium cations. The hydration and dehydration of I are studied by thermal analysis and high-temperature X-ray diffraction. The dehydration is accompanied by decomposition of the starting crystal hydrate to give intermediate compounds. Anhydrous compound I undergoes a reversible phase transition at 740°C. The high-temperature phase is assumed to have a hexagonal unit cell (a = 6.169(4) Å, c = 15.72(1) Å, Z = 2).     

Crystal-structure refinement, thermal expansion, and chemical distortion of Bi2Ga4O9

Single crystals of Bi₂Ga₄O₉ are grown from a solution in a bismuth oxide melt. The structure (orthorhombic, space group Pbam, a = 7.918(2) Å, b = 8.299(2) Å, c = 5.894(2) Å, Z = 2) is refined to R = 0.052 in the anisotropic approximation based on single-crystal X-ray diffraction data. The structure is a framework. The bismuth(III) atoms are sixfold coordinated; gallium(III) exists in both tetrahedral and octahedral coordinations. The thermal expansion of Bi₂Ga₄O₉ is studied by high-temperature X-ray powder diffraction method and is found to be sharply anisotropic. A structural interpretation of the anisotropy is proposed. Chemical distortion in the Bi₂M₄O₉ compounds with M = Fe(III), Al, or Ga is analyzed and compared with the thermal expansion of Bi₂Ga₄O₉.     

[M(NH3)5Cl]WO4 (M = Cr, Rh): Synthesis, crystal structure, thermal properties

By single crystal X-ray diffraction the crystal structure of a series of [M(NH₃)₅Cl]WO₄ (M = Cr, Rh) complex salts is determined. The features of thermal expansion of the single crystal of [Cr(NH₃)₅Cl]WO₄ are studied by low- and high-temperature X-ray diffractometry in the temperature range from ?173°C to +127°C. It is shown that with an increase in the temperature, W-O distances and ∠O-W-O bond angles equalize and the average W-O distances decrease by 0.012 Å. The thermal properties of the salts in different gaseous atmospheres are examined and the phase composition of the obtained products is studied.     

Crystal structures of α- and β-EuPrCuS3

The crystal structure of the EuPrCuS₃ complex sulfide synthesized for the first time has been solved by X-ray powder diffraction. Crystals are orthorhombic, space group Pnma. EuPrCuS₃ has two polymorphs: the high-temperature phase of Ba₂MnS₃ structural type with unit cell parameters a = 8.0786(1) Å, b = 4.0288(1) Å, and c = 15.8389(2) Å and the low-temperature phase of BaLaCuS₃-isostructural with unit cell parameters a = 11.0819(2) Å, b = 4.0710(1) Å, and c = 11.4459(3) Å.     

EuNdCuS3: Crystal structure of the high-temperature polymorph and properties

The X-ray diffraction structure of the high-temperature polymorph of complex sulfide EuNdCuS₃ is determined. The phase we prepared has an orthorhombic structure with the unit cell parameters a = 8.0648(3) Å, b = 4.0207(1) Å, c = 15.7924(3) Å, space group Pnma, Z = 4, Ba₂MnS₃ type structure. The sample is IR transparent in the range 1800–2800 cm^?1. Thermal expansion coefficient is found to experience jumps, which are characteristic of phase transitions.     

The crystal structure of Pd2B

The crystal structure of Pd₂B has been investigated by X-ray powder diffraction and single-crystal diffractometry. There are strong indications that Pd₂B crystallizes with the anti-CaCl₂ type structure (C 35), space group Pnnm (No. 58), a = 4.6918(4) Å, b = 5.1271(4) Å, and c = 3.1096(3) Å, but the extent to which the boron atoms assume ordered positions cannot be determined precisely with X-ray diffraction methods alone.     

Synthesis and Physicochemical Properties of a Lanthanum-Containing Analog of the Mineral Berthierite FeSb<Subscript>2</Subscript>S<Subscript>4</Subscript>

Phase equilibria in the FeSb₂S₄–FeLa₂S₄ system were studied by physicochemical analysis methods (differential thermal, X-ray powder diffraction, and microstructural analyses and microhardness and density measurements), and the phase diagram of the system was constructed. The formation of quaternary sulfide FeLaSbS₄ melting congruently at 1230 K, an analog of the mineral berthierite FeSb₂S₄, was detected. The X-ray powder diffraction analysis showed that FeLaSbS₄ belongs to the berthierite structural type and crystallizes in the orthorhombic system with the unit cell parameters a = 11.424 Å, b = 14.160 Å, c = 3.782 Å, Z = 4, and space group Pbam.     

Synthesis,crystal structure,and thermal properties of [Pd(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>][AuCl<Subscript>4</Subscript>]<Subscript>2</Subscript>

The double complex salt [Pd(NH₃)₄][AuCl₄]₂ was synthesized and studied by X-ray diffraction: a = 7.5234(6) Å, b = 7.7909(5) Å, c = 8.0247(6) Å, α = 108.483(2)°, β = 106.497(2)°, γ = 99.972(3)°, V = 409.43(5) ų, space group P \(\overline 1 \), Z = 1, ρ_calod = 3.456 g/cm³, R = 0.0267. The compound was characterized by powder X-ray diffraction, thermal analysis, and IR and Raman spectroscopy. The metal products of thermolysis of the complex were studied by powder X-ray diffraction.     

Crystal Structures of α- and β-SrCeCuS<Subscript>3</Subscript>

The crystal structure of SrCeCuS₃, a complex sulfide synthesized for the first time, has been solved using X-ray powder diffraction data. The crystals are orthorhombic, space group Pnma. SrCeCuS₃ has two polymorphs: the high-temperature phase of Ba₂MnS₃ structural type (a = 8.1393(3) Å, b = 4.0587(2) Å, c = 15.9661(2) Å) and the low-temperature phase isostructural to BaLaCuS₃ (a = 11.1626(2) Å, b = 4.0970(2) Å, c = 11.5307(1) Å). The incongruent melting temperature and enthalpy of SrCeCuS₃ are, respectively, 1486 ± 3 K and 13.4 ± 1.5 J/g.     

Neutron and X-ray diffraction study on polymorphism in lithium orthotantalate,Li3TaO4

The structures of the low-and high-temperature modifications of lithium orthotantalate, Li₃TaO₄, have been determined by neutron and X-ray diffraction methods. The low-temperature, or β, phase has symmetry $\text{C2}\text{c}$ and lattice parameters a₁ = 8.500(3), b₁ = 8.500(3), c₁ = 9.344(3)Å, and β = 117.05(2)°. The high-temperature, or α, phase has symmetry P2 and lattice parameters a_h = 6.018(1), b_h = 5.995(1), c_h = 12.865(2)Å, and β_h = 103.53(2)°. Both structures are ordered. The β-phase has a rock salt-type structure with a 3 : 1 ordering of the Li⁺ and Ta⁵⁺ ions. Its structure can be generated from the low-temperature modification by means of a complex pattern of shifts of the Ta⁵⁺ ions.     

Compound formation in the System PbGeO3?Pb5Ge3O11

Compound formation in the system PbGeO₃? Pb₅Ge₃O₁₁ was studied by thermal analysis and high-temperature X-ray diffraction. New modifications of PbGeO₃ and Pb₅Ge₃O₁₁ were prepared by the simultaneous hydrolysis of lead and germanium alkoxides, followed by washing and drying; the former has a hexagonal unit cell with a = 15.573 Å and c = 7.240 Å, and the latter has an orthorhombic crystal structure with a = 5.081 Å, b = 7.301 Å and c = 8.817 Å. They are transformed to the known monoclinic and hexagonal modifications at 575 to 610°C and 410 to 450°C, respectively. No compound of Pb₃Ge₂O₇ was confirmed. The structures of germanate groups in the lead germanate compounds are discussed on the basis of the infrared spectral data.     

Synthesis and characterization of a newly designed di-copper(II)-based complex and study of its artificial enzyme catalytic activity

A di-copper(II) complex of the formula [(dien)Cu(μ-1,6-DAH)Cu(dien)(NO₃)₂](NO₃)₂, where μ-1,6-DAH = 1,6-diaminohexane, has been synthesized and characterized by X-ray crystallography, X-ray powder diffraction, thermal gravimetric (TG) and differential thermal analyses, cyclic voltammetry, infrared, ultraviolet visible spectroscopies and elemental analysis methods. It was crystallized in a monoclinic system, space group P2₁/n, with a = 8.0297(8) Å, b = 12.4937(14) Å, c = 15.3786(15) Å, β = 102.739(8) Å and z = 2. Each copper(II) has a square-based pyramidal coordination geometry with four N atoms building the basal plane (three from dien and one from μ-1,6-DAH). TGA study of the complex revealed the compound to be stable up to 245 °C. Electrochemical behavior of complex and enzyme-like catalytic activity of this complex, as a potential functional model for the active site of tyrosinase, was studied extensively. Kinetic studies show that the complex has the maximum enzymatic activity at pH 8, temperature of 40 °C and ionic strength of 50 mM.     

Effect of hydrothermal treatment on the composition and structure of Pt(IV) hydroxo complexes as model precursors of the active component in Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

The influence of hydrothermal treatment conditions (temperature, duration, acidity of the medium) on the structural and chemical transformations of the complex H₂[Pt(OH)₆] was studied. The composition and structure of the resulting compounds were determined by several physicochemical methods. Thermal analysis coupled with mass spectrometry showed that, as the hydrothermal treatment temperature is raised from 25 to 120 and 150°C, the product composition in terms of empirical formulas changes as follows: PtO₂ · 4H₂O → PtO₂ · 3.5H₂O → PtO₂ · 1.5H₂O. X-ray diffraction and UV and IR spectroscopy demonstrated that the changes in the chemical composition are accompanied by the amorphization of the structure and Pt-O bond strengthening. X-ray structure determination using the radial electron density distribution method showed that polynuclear species ～10–15 Å in size with a structure similar to that of orthorhombic PtO₂ form in the complexes subjected to “hard” hydrothermal treatment (T ≥ 150°C).     

The crystal structure of CuAsSe0.8S0.2 and related compounds

The structure of CuAsSe_xS_1?x in the composition range 0.5 < x < 0.9 has been determined by single-crystal X-ray and electron diffraction and high-resolution electron microscopy. CuAsSe_0.8S_0.2 is found to be orthorhombic with space group Pbcn and unit cell dimensions a = 11.66 ± 0.02 åA, b = 6.73 ± 0.01 Å, and c = 25.41 ± 0.03 Å. The structure was inferred by comparing the electron and X-ray diffraction patterns with those from CuAsSe, and was isotropically refined to R = 0.16 for 287 observed X-ray reflections. High-resolution electron microscopy was used to confirm the structure by matching observed and calculated images and to show the presence of stacking faults in the crystals. The atomic positions of CuAsSe_0.8S_0.2 are related to the 8HZnS polytype structure. In Jagodzinski nomenclature it has hccchccc stacking. Powder X-ray and single crystal electron diffraction patterns of CuAsSe_0.75S_0.25 and CuAsSe_0.9S_0.1 were consistent with the same structure-type. Single-crystal X-ray diffraction of CuAsSe_0.6S_0.4 showed it to be isostructural with CuAsS with orthorhombic space group Pnam and unit cell dimensions a = 11.59 ± 0.02 Å, b = 5.56 ± 0.01 Å, and c = 3.827 ± 0.005 Å. The same structure-type was found for CuAsSe_0.5S_0.5 and CuAsSe_0.67S_0.33 using X-ray powder diffraction.     

The interaction of aromatic hydrocarbons with organometallic compounds of the main group elements. : IV. The preparation and structure of the novel selenide K[CH3Se{Al(CH3)3}3] · 2C6H6

The crystal structure of K[CH₃Se {Al(CH₃)₃}₃] · 2C₆H₆ has been determined from single-crystal X-ray diffraction data collected by counter methods. The compound crystallizes in the triclinic space group P$\text{1}$ with cell dimensions a = 17.165(7), b = 10.144(7), c = 10.156(7)Å, α = 119.26(5), β = 104.07(5), ψ = 80.51(5)°, and Dc = 1.12 gcm^?3 for Z = 2. Least-squares refinement gave a final R value of 0.083 for 1967 independent observed reflections. One of the two benzene molecules in the asymmetric unit has been located by difference Fourier techniques. Because of either extreme disorder or high thermal motion, the aromatics make practically no contribution to the X-ray scattering. The selenium atom in the anion exhibits tetrahedral coordination. The Al-Se bond lengths average 2.578(5)Å, and the Se-C distance is 1.93(2)Å.     

Structures of two high-temperature Dy2TiO5 modifications

Single crystals of two structural modifications of high-temperature dysprosium titanate Dy₂TiO were grown. Using X-ray diffraction, the crystal structure of the cubic modification (space group Fd3m, a = 10.28(1)Å, Z = 10.4) was refined and the structure of a new monoclinic modification (space group B2/m, a = 10.33(1)Å, b = 3.653(5)Å, c = 7.306(6)Å, β = 90.00(7)°, Z = 2.4), which crystallizes in minor amounts together with the cubic phase, was determined. The lowering of symmetry from cubic to monoclinic is due to different distributions of the Dy³⁺ and Ti⁴⁺ cations over the sites present in the cubic cell.     

Hydrate formation in the system n-propanol–water

The phase diagram of the binary system n-propanol alcohol–water was investigated with use of differential thermal analysis and powder X-ray diffraction. The phase diagram has three groups of thermal effects, which can be considered as peritectic melting of three different hydrates (?60.0, ?53.5, and ?41.5 °C). At the same time, powder X-ray diffraction data indicate the existence of only one compound in this system (cubic unit cell, a = 12.09 ± 0.01 Å and 12.15 ± 0.01 Å at ?109 to ?66 °C, respectively). The most probable explanation of this contradiction seems to be the existence of several hydrates belonging to the same structural type but different in composition.     

Thermal decomposition of silver carbonate

Conflicting results have been reported by different workers on the thermal decomposition of silver carbonate, Ag₂CO₃. In the present study, the decomposition mechanism was elucidated by various analytical methods; gas analysis (differential thermal gas analyses) in helium, carbon dioxide and oxygen flows with and without a P₂O₅ trap or a KOH trap, DTA-TG in a carbon dioxide flow and high-temperature X-ray diffraction analysis in a carbon dioxide flow. The gas evolution at ca. 200?C consisted of carbon dioxide. A simultaneous evolution of carbon dioxide and oxygen occurred at ca. 400?C. Two endothermic peaks (ca. 189 and 197?C) without weight change during the heating in a carbon dioxide atmosphere were due to the phase transition of silver carbonate from the normal viaΒ toα phase. The reverse transition occurred during the cooling.     

A novel interpenetrating 2-D brush-like structure: hydrothermal synthesis and crystal structure of [Cu(phen)V4O10]∞ (phen=1,10-phenanthroline)

A novel vanadium oxide, [Cu(phen)V₄O₁₀]_∞ (1), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR, EPR spectroscopy and thermal analysis. The compound crystallizes in monoclinic structure of P2₁/m with a=7.4169(10) Å, b=10.0460(13) Å, c=11.0845(15) Å, β=102.520(2)°, V=806.27(19) Å³ and Z=2.     

Structure of bis-(1,1,1-trifluoro-2-(methylimino)pentanoato-4)copper(II). Thermal properties of N-methylsubstituted copper(II) β-iminoketonates

The single crystal X-ray diffraction (XRD) method was used to determine the structure of the [Cu(mi-tfac)₂] (mi-tfac = MeC(O)CHC(NMe)CF₃) complex at the temperature of 150 K. The crystallographic data are as follows: space group Pnna, a = 11.8798(16) Å, b = 12.0315(16) Å, c = 10.6259(14) Å, V = 1518.8(4) ų, Z = 4, R = 0.0288. The structure is molecular, the coordination environment of copper in the molecule adopts a distorted tetrahedral geometry. The Cu–O and Cu–N distances are 1.9182(13) Å and 1.9610(16) Å respectively, the OCuN chelate angle is 94.18(5)°. The thermal properties of the compounds [Cu(mi-tfac)₂] and [Cu(RC(O)CHC(NMe)R)₂] (R = Me, ^t Bu) in the condensed phase have been studied by the methods of thermogravimetry and differential scanning calorimetry. The thermodynamic characteristics of the melting processes have been determined.