Crystal structure of [CH<Subscript>3</Subscript>NH<Subscript>3</Subscript>][(UO<Subscript>2</Subscript>)(H<Subscript>2</Subscript>AsO<Subscript>4</Subscript>)<Subscript>3</Subscript>]

The crystal structure of a previously unknown compound [CH₃NH₃][(UO₂)(H₂AsO₄)₃] was solved by direct methods and refined to R ₁ = 0.038 for 3041 reflections with |F _hkl | >-4σ |F _hkl |. The compound crystallizes in the monoclinic system, space group P2₁/c, a = 8.980(1), b = 21.767(2), c = 7.867(1) Å, β = 115.919(5)°, V = 1383.1(3) ų, Z = 4. In the structure of the compound, pentagonal bipyramids of uranyl ions, sharing bridging atoms with tetrahedral [H₂AsO₄]^? anions, form strongly corrugated layered complexes [(UO₂)(H₂AsO₄)₃]^? arranged parallel to the (100) plane. The protonated methylamine molecules [CH₃NH₃]⁺ form unidimensional tapelike packings parallel to the c axis and linked by hydrophilic-hydro-phobic interactions. The topology of the layered uranyl arsenate complex [(UO₂)(H₂AsO₄)₃]^? is unusual for uranyl compounds and was not observed previously. A specific feature of this topology is the presence of monodentate arsenate “branches” arranged within the layer.     

Synthesis and structure of (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>[UO<Subscript>2</Subscript>(CH<Subscript>3</Subscript>COO)<Subscript>3</Subscript>]<Subscript>2</Subscript>(NCS)

The compound (NH₄)₃[UO₂(CH₃COO)₃]₂(NCS) (I) was synthesized and examined by single crystal X-ray diffraction analysis. The compound crystallizes in the rhombic system with the unit cell parameters a = 11.5546(4), b = 18.5548(7), c = 6.7222(3) Å, V = 1441.19(10) ų, space group P2₁2₁2, Z = 2, R = 0.0345. The uranium-containing structural units of crystals of I are isolated mononuclear groups [UO₂(CH₃COO)₃]^? belonging to crystal-chemical group AB ₃ ⁰¹ (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?) of uranyl complexes. The specific features of packing of the uranium-containing complexes in the crystal structure are considered.     

Compounds WAl<Subscript>4</Subscript>, WAl<Subscript>3</Subscript>, W<Subscript>3</Subscript>Al<Subscript>7</Subscript>, and WAl<Subscript>2</Subscript> and Al-W-N combustion products

X-ray diffraction data are presented for combustion products in the Al-W-N system. New, nonequilibrium intermetallic compounds have been identified, their diffraction patterns have been indexed, and their unit-cell parameters have been determined. The phases α-and β-WAl₄ are shown to exist in three isomorphous forms, differing in unit-cell centering. The phases α′-, α″-, and α?-WAl₄ are monoclinic, with a ₀ = 5.272 Å, b ₀ = 17.770 Å, c ₀ = 5.218 Å, β = 100.10°; point groups C12/c1, A12/n1, I12/a1, respectively. The phases β′-, β″-, and β?-WAl₄ are monoclinic, with a ₀ = 5.465 Å, b ₀ = 12.814 Å, c ₀ = 5.428 Å, β = 105.92°; point groups A112/m, B112/m, I112/m, respectively. The compounds WAl₂ and W₃Al₇, identified each in two isomorphous forms, differ in cell metrics (doubling) but possess the same point group: P222. WAl ₂ ^′ : orthorhombic, a ₀ = 5.793 Å, b ₀ = 3.740 Å, c ₀ = 6.852 Å. WAl ₂ ^″ : orthorhombic, a ₀ = 11.586 Å, b ₀ = 3.740 Å, c ₀ = 6.852 Å. W₃Al ₇ ^′ : orthorhombic, Pmm2, a ₀ = 6.225 Å, b ₀ = 4.806 Å, c ₀ = 4.437 Å. W₃Al ₇ ^″ : orthorhombic, Pmm2, a ₀ = 12.500 Å, b ₀ = 4.806 Å, c ₀ = 8.874 Å. The new phase WAl₃: triclinic, P1, a ₀ = 8.642 Å, b ₀ = 10.872 Å, c ₀ = 5.478 Å, α = 104.02°, β = 64.90°, γ = 107.15°.     

Crystal and molecular structure of uranyl acetylacetonate dimer, [UO<Subscript>2</Subscript>(C<Subscript>5</Subscript>H<Subscript>7</Subscript>O<Subscript>2</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>

The crystal and molecular structure of uranyl acetylacetonate dimer was determined by single crystal X-ray diffraction. The compound crystallizes in the tetragonal system, a = 7.9420(2), c = 40.1240(13) Å (at 100 K), Z = 4, space group P4₁2₁2. Dimeric uranyl acetylacetonate molecules in the crystal are formed by bridging bonding of one of O atoms of the acetylacetonate ligands with U atoms, so that the coordination polyhedra of U atoms (distorted pentagonal bipyramids) share a common equatorial edge. The dimer has a nonplanar structure, being significantly bent along the conventional line connecting the bridging O atoms.     

Synthesis and characterization of ternary compound,Mn<Subscript>2</Subscript>SnTe<Subscript>4</Subscript>

Mn₂SnTe₄ was synthesized by direct fusion using the anneal method. X-ray powder diffraction analysis indicated that this material crystallizes in the olivine-type structure, space group Pnma, Z = 4, with unit cell parameters: a = 14.020(2) Å, b = 8.147(1) Å, c = 6.607(1) Å, V = 754.7(2) ų. The Rietveld refinement converged to the figures of merit, R _p = 6.9%, R _wp = 8.5%, R _exp = 6.0%, χ² = 2.0 and S = 1.4.     

High-temperature crystal chemistry of Na<Subscript>6</Subscript>(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>O(MoO<Subscript>4</Subscript>)<Subscript>4</Subscript>

Thermal deformations of Na₆(UO₂)₂O(MoO₄)₄ were studied by high-temperature powder X-ray diffraction. The compound crystallizes in the triclinic system, space group Р\(\bar 1\), a = 7.636(7), b = 8.163(6), c = 8.746(4) Å, α = 72.32(9)°, β = 79.36(4)°, γ = 65.79(5)°, V = 472.74(4) ų. It is stable in the temperature interval 20–700°С. The thermal expansion coefficients (TECs) are α₁₁ = 25.5 × 10^–6, α₂₂ = 7.8 × 10^–6, and α₃₃ = 1.1 × 10^–6 (°C)^–1. The orientation of the TEC pattern relative to the crystallographic axes is a₃₃^Z = 45°, a₃₃^X = 122°, a₂₂^Z = 59°, and a₂₂^X = 66°. The anisotropy of the thermal expansion is due to specific features of the crystal structure of the compound.     

Synthesis and crystal structure of [UO<Subscript>2</Subscript>(OH)(CO(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>)<Subscript>3</Subscript>]<Subscript>2</Subscript>(ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The complex [UO₂(OH)(CO(NH₂)₂)₃]₂(ClO₄)₂ (I) was synthesized. A single crystal X-ray diffraction study showed that compound I crystallizes in the triclinic system with the unit cell parameters a = 7.1410(2), b = 10.1097(2), c = 11.0240(4) Å, α = 104.648(1)°, β = 103.088(1)°, γ = 108.549(1)°, space group \(P\bar 1\), Z = 1, R = 0.0193. The uranium-containing structural units of the crystals are binuclear groups [UO₂(OH)· (CO(NH₂)₂)₃] ₂ ²⁺ belonging to crystal-chemical group AM²M ₃ ¹ [A = UO ₂ ²⁺ , M² = OH^?, M¹ = CO(NH₂)₂] of uranyl complexes. The crystal-chemical analysis of nonvalent interactions using the method of molecular Voronoi-Dirichlet polyhedra was performed, and the IR spectra of crystals of I were analyzed.     

Preparation and crystal structure characterization of CuNiGaSe<Subscript>3</Subscript> and CuNiInSe<Subscript>3</Subscript> quaternary compounds

Samples of the quaternary chalcogenide compounds, CuNiGaSe₃ and CuNiInSe₃, prepared by direct fusion and annealing method, were characterized by X-ray powder diffraction. In each case, the crystal structure was refined using the Rietveld method. Both compounds were found to crystallize in the tetragonal system, space group P \(\bar 4\)2c (N°112), with unit cell parameter values a = 5.6213(1) Å, c = 11.0282(3) Å, V = 348.48(1) ų and a = 5.7857(2) Å, c = 11.6287(5) Å, V = 389.26(3) ų for CuNiGaSe₃ and CuNiInSe₃, respectively. These compounds have a normal adamantane structures and are isostructural with CuFeInSe₃.     

Anomalous Impact of Hydrostatic Pressure on Superconductivity of Polycrystalline LaO<Subscript>0.5</Subscript>F<Subscript>0.5</Subscript>BiSe<Subscript>2</Subscript>

We report bulk superconductivity at 2.5 K in LaO_0.5F_0.5BiSe₂ compound through the DC magnetic susceptibility and electrical resistivity measurements. The synthesized LaO_0.5F_0.5BiSe₂ compound is crystallized in tetragonal structure with space group P4/nmm and Reitveld refined lattice parameters are a = 4.15(1) Å and c = 14.02(2) Å. The lower critical field of H _c1 = 40 Oe, at temperature 2 K is estimated through the low field magnetization measurements. The LaO_0.5F_0.5BiSe₂ compound showed metallic normal state electrical resistivity with residual resistivity value of 1.35 m Ω cm. The compound is a type-II superconductor, and the estimated H _c2(0) value obtained by WHH formula is above 20 kOe for 90 % ρ _n criteria. The superconducting transition temperature decreases with applied pressure till around 1.68 GPa and with further higher pressures a high- T _c phase emerges with possible onset T _c of above 5 K for 2.5 GPa.     

Critical Behavior of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>0.95</Subscript>Fe<Subscript>0.05</Subscript>O<Subscript>3</Subscript> Manganite

The critical behavior of perovskite manganite La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ at the ferromagnetic–paramagnetic has been analyzed. The results show that the sample exhibited the second-order magnetic phase transition. The estimated critical exponents derived from the magnetic data using various such as modified d’Arrott plot Kouvel–Fisher method and critical magnetization M(T _C, H). The critical exponents values for the La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ are close to those expected from the mean field model β = 0.504 ± 0.01 with T _C = 275661 ± 0.447 (from the temperature dependence of the spontaneous magnetization below T _C ), γ = 1.013 ± 0.017 with T _C = 276132 ± 0.452 (from the temperature dependence of the inverse initial susceptibility above T _C ), and δ = 3.0403 ± 0.0003. Moreover, the critical exponents also obey the single scaling equation of M(H, ε) = |ε| ^β f _±(H/|ε| ^β+γ ).     

Synthesis and structure of the CsSmP<Subscript>4</Subscript>O<Subscript>12</Subscript> cyclotetraphosphate (cubic CsNdP<Subscript>4</Subscript>O<Subscript>12</Subscript> structure)

CsSmP₄O₁₂ crystals have been prepared at 300°C in molten polyphosphoric acids containing Cs, Mg, and Sm cations, and their crystal structure has been determined: sp. gr. I \(\bar 4\) 3d, a = 15.1225(8) Å, Z = 12, CsNdP₄O₁₂ structure.     

Phase relations in the Ag<Subscript>8</Subscript>SnS<Subscript>6</Subscript>-Ag<Subscript>2</Subscript>SnS<Subscript>3</Subscript>-AgBr system and crystal structure of Ag<Subscript>6</Subscript>SnS<Subscript>4</Subscript>Br<Subscript>2</Subscript>

The T-x phase diagram of the Ag-Sn-S-Br system has been studied in the composition region Ag₈SnS₆-Ag₂SnS₃-AgBr, and a compound of composition Ag₆SnS₄Br₂ has been identified. Ag₆SnS₄Br₂ has a new structure, closely related to that of Ag₆GeS₄Br₂: sp. gr. Pnma, a = 6.67050(10), b = 7.82095(9), c = 23.1404(3) Å, Z = 4, R _B = 0.0519, R _wp = 0.0782, χ² = 1.36.     

Crystal structures of Ln<Subscript>2</Subscript>TiO<Subscript>5</Subscript> (Ln = Gd,Dy) polymorphs

Single crystals of four Ln₂TiO₅ polymorphs have been grown, and their structures have been determined: orthorhombic (Gd₂TiO₅, a = 10.460(5), b = 11.317(6), c = 3.750(3) Å, Pnam, Z = 4), hexagonal (Gd_1.8Lu_0.2TiO₅, a = 3.663(3), c = 11.98(1) Å, P6₃/mmc, Z = 1.2), cubic (Dy₂TiO₅, a = 10.28(1) Å, Fd3m, Z = 10.4), and monoclinic (Dy₂TiO₅, a = 10.33(1), b = 3.653(5), c = 7.306(6) Å, β = 90.00(7)°, B2/m, Z = 2.4). The last polymorph has been identified for the first time.     

Synthesis and Superconductivity of Layered Compounds with Orthogonal [Zr<Subscript>2</Subscript>N<Subscript>2</Subscript>] Network

Layered α-form ZrNX (X: Cl and Br) compounds with high quality were prepared by chemical vapor transport. The intercalation of alkali metal A (A: Li, Na, K, Rb) was carried out to realize electron doping into the orthogonal [Zr₂N₂] layers. The Rietveld refinement analysis reveals that the [Zr₂N₂] crystalline layers in the intercalation compounds shift mutually in the ab plane when compared with the hosts. Magnetic measurements show that the intercalation compounds A _x ZrNX are changed into superconductors with transition temperature T _c of up to 12 K. Upon the cointercalation of solvent molecules such as THF, T _c decreases to as low as 6.1 K with increasing the interlayer spacing d up to 14 Å, which is similar to the d dependence of T _c recently found in electron-doped α-form TiNX series. We also succeeded in synthesizing another new polymorph of α-Zr₂N₂S by the topochemical reaction between α-form ZrNX and Na₂S. α-Zr₂N₂S (space group: Immm, a = 4.1375(1) Å, b = 3.5422(1) Å, and c = 11.5204(3) Å) has the same α-[Zr₂N₂] layers, whereas the interlayer spacing between two adjacent [Zr₂N₂] layers is effectively decreased by 1/3 when compared with the parent compounds of ZrNX.     

Ionic conductivity of BaF<Subscript>2</Subscript> + ZnF<Subscript>2</Subscript> + CdF<Subscript>2</Subscript> + YbF<Subscript>3</Subscript> optical fluoride ceramic

The electrical conductivity of an optical fluoride ceramic in the quaternary system BaF₂ + ZnF₂ + CdF₂ + YbF₃ has been determined in the temperature range 338–722 K using impedance spectroscopy (5 to 5 × 10⁵ Hz). The 500-K ionic conductivity of the ceramic is σ = 3.3 × 10^–4 S/cm, which corresponds to the electrical characteristics of single crystals of the best conducting nonstoichiometric M_1–x R _x F_{2 + x} (M = Sr, Ba; R = La–Nd; x = 0.3–0.5) fluorite phases. We have observed nonmonotonic variation (breaks) in temperature-dependent σ, which is due to competing fluoride ion transport processes in different parts of the ceramic sample. The highly conductive state of the BaF₂ + ZnF₂ + CdF₂ + YbF₃ fluoride ceramic seems to be due to the formation of structural regions corresponding to a Ba_1–x Yb _x F_{2 + x} solid solution.     

Ho<Subscript>2</Subscript>S<Subscript>3</Subscript>-Ga<Subscript>2</Subscript>S<Subscript>3</Subscript> phase diagram

The Ho₂S₃-Ga₂S₃ system has been studied using differential thermal analysis, X-ray diffraction, microstructural analysis, microhardness tests, and density measurements, and its phase diagram has been constructed. The system contains three ternary compounds: Ho₃GaS₆, HoGaS₃, and Ho₆Ga_10/3S₁₄. Their melting behavior has been studied for the first time. The compound Ho₆Ga_10/3S₁₄ melts congruently at 1435 K; Ho₃GaS₆ and HoGaS₃ melt incongruently at 1370 and 1250 K, respectively. The Ho₂S₃-Ga₂S₃ system is a pseudobinary join of the ternary system Ho-Ga-S. At room temperature, the β-Ga₂S₃-based solid solution extends to 1.5 mol % Ho₂S₃; the Ho₂S₃ solubility in γ-Ga₂S₃ is 10 mol %. The compounds HoGaS₃ and Ho₃GaS₆ crystallize in orthorhombic symmetry (Ho₃GaS₆: a = 10.40 Å, b = 13.20 Å, c = 6.44 Å, Z = 4; HoGaS₃: a = 6.8 Å, b = 9.92 Å, a = 3.08 Å, Z = 4). Ho₆Ga_10/3S₁₄ has a hexagonal structure (a = 9.62 Å, c = 6.04 Å).     

Effect of Al Substitution in Structural and Magnetic Properties of MnCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

Single-phase samples of Mn(Cr_1?x Al _x )₂O₄ (x = 0 – 0.30) with cubic spinel structure were prepared and the lattice constant is found to decrease from a = 8.4396 Å for x = 0 to a = 8.3801 Å for x = 0.30. The substitution of Al at Cr site is confirmed from the blue shift of Raman modes. Magnetization measurements and analysis show all the prepared samples exhibit ferrimagnetic transition with transition temperature in the range of 46 K for x = 0 to 33 K for x = 0.30. The saturation magnetization (M _s ) and the estimated anisotropy constant (K) show an anomalous behavior up to x = 0.10 and beyond that they decrease monotonously. They are explained by considering different site preferences of Al ³⁺ ions as the doping concentration is increased. The theoretical and experimental effective magnetic moment of the samples is found to be comparable and it decreases with increase in Al concentration.     

Crystal and molecular structure of [TcCl(CO)<Subscript>5</Subscript>] and [TcBr(CO)<Subscript>5</Subscript>]. Correlations with the reactivity and electronic structure

The crystal and molecular structures of [TcCl(CO)₅] and [TcBr(CO)₅] were determined. The compounds crystallize in the rhombic system, space group Pnma; a = 11.6757(18) and 11.9564(18) Å, b = 11.7365(14) and 11.7250(18) Å, c = 6.0407(7) and 6.2020(15) Å, V = 827.77(19) and 869.5(3) ų, respectively; Z = 4. The structural data for pentacarbonyl halides were compared in the series Mn-Tc-Re and Cl-Br-I. Quantum-chemical calculations of the compounds [TcX(CO)₅] (X = F, Cl, Br, I) and of the anion [TcCl₃(CO)₃]^2? were made. A correlation between the geometry, electronic structure, and reactivity of the complexes is considered.     

Synthesis and Crystal Structures of New Layered Uranyl Compounds Containing Dimers [(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>O<Subscript>8</Subscript>] of Edge-Linked Pentagonal Bipyramids

Two new U(VI) compounds, [((CH₃)₂CHNH₃)(CH₃NH₃)][(UO₂)₂(CrO₄)₃] (1) and [CH₃NH₃][(UO₂)· (SO₄)(OH)] (2), were prepared by combining hydrothermal synthesis with isothermal evaporation. Compound 1 crystallizes in the monoclinic system, space group Р2₁, a = 9.3335(19), b = 10.641(2), c = 9.436(2) Å, β = 94.040(4)°. Compound 2 crystallizes in the rhombic system, space group Рbca, a = 11.5951(8), b = 9.2848(6), c = 14.5565(9) Å. The structures of the compounds were solved by the direct methods and refined to R₁ = 0.041 [for 5565 reflections with Fo > 4σ(Fo)] and 0.033 [for 1792 reflections with Fo > 4σ(Fo)] for 1 and 2, respectively. Single crystal measurements were performed at 296 and 100 K for 1 and 2, respectively. The crystal structure of 1 is based on [(UO₂)₂(CrO₄)₃]^2– layers, and that of 2, on [(UO₂)(SO₄)(OH)]^– layers. Both kinds of layers are constructed in accordance with a common principle and are topologically similar. Protonated isopropylamine and methylamine molecules are arranged between the layers in 1, and protonated methylamine molecules, in 2. Compound 1 is the second known example of a U(VI) compound templated with two different organic molecules simultaneously.     

Fluorination of Bi<Subscript>1.8</Subscript>Fe<Subscript>1.2</Subscript>SbO<Subscript>7</Subscript> pyrochlore solid solutions

A technique has been developed for fluorinating the pyrochlore oxide Bi_1.8Fe_0.2FeSbO₇, and a compound with the composition Bi_1.8Fe_1.2SbO_7–x/2F_x has been obtained. The synthesized oxyfluoride also has the pyrochlore structure (sp. gr. Fd3m), with a lattice parameter a = 10.4443(1) Å (R _wp = 5.2). It has been shown that the charge balance upon fluorine substitution for oxygen is maintained not through partial reduction of Fe³⁺ to Fe²⁺ but through the incorporation of fluorine into oxygen vacancies. The magnetic behavior of the fluorinated pyrochlore phase is determined by the persisting frustration of the octahedral sublattice, which is responsible for the development of a spin glass state below T _f = 12 K. The fluorination-induced changes in the anion sublattice led to an increase in the antiferromagnetic exchange interaction between neighboring Fe³⁺ ions and changes in the dynamic properties of the spin glass phase.