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.     

Crystal structure of KNa<Subscript>3</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>5</Subscript>O<Subscript>6</Subscript>(SO<Subscript>4</Subscript>)]

The crystal structure of a previously unknown compound KNa₃[(UO₂)₅O₆(SO₄)] [space group Pbca, a = 13.2855(15), b = 13.7258(18), c = 19.712(2) Å, V = 3594.6(7) ų] was solved by direct methods and refined to R ₁ = 0.055 for 3022 reflections with |F _hkl | ≥ 4σ |F _hkl |. In the structure there are five sym-metrically nonequivalent uranyl cations. They are linked by cationcation (CC) interactions to form a pentamer whose central cation is U(2)O ₂ ²⁺ forming two three-centered CC bonds. All the uranyl ions are coordinated in the equatorial plane by five O atoms, which leads to the formation of pentagonal bipyramids sharing common edges to form layers parallel to the (100) plane. The sulfate tetrahedron links the uranyl layers into a 3D framework. The K⁺ and Na⁺ cations are arranged in framework voids. A brief review of CC interactions in U(VI) compounds is presented.     

Crystal structure of a complex of Pu(VI) nitrate with triphenylphosphine oxide, [PuO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>(OP(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)<Subscript>3</Subscript>)<Subscript>2</Subscript>]

Single crystals of [PuO₂(NO₃)₂(TPPO)₂] (TPPO = OPPh₃) isostructural to the related compounds of uranyl and neptunyl were isolated, and the structure of this complex was determined. Contrary to the complexes [AnO₂(TPPO)₄](ClO₄)₂ studied previously, the interatomic distances and volumes of coordination polyhedra of An in these compounds somewhat decrease in the series U-Np-Pu. This difference was attributed to a change in the number of TPPO ligands in the compounds and weakening of their interaction with oxygen atoms of the AnO ₂ ²⁺ groups in passing from [AnO₂(TPPO)₂](ClO₄)₂ to [AnO₂(No₃)₂(TPPO)₂].     

Synthesis and crystal structure of Cu<Subscript>2</Subscript>{(UO<Subscript>2</Subscript>)<Subscript>3</Subscript>[(S,Cr)O<Subscript>4</Subscript>]<Subscript>5</Subscript>}(H<Subscript>2</Subscript>O)<Subscript>17</Subscript>

Cu₂{(UO₂)₃[(S,Cr)O₄]₅}(H₂O)₁₇ crystals were prepared by evaporation of aqueous solutions. The crystal structure was solved by the direct method and refined to R ₁ = 0.064 (wR ₂ = 0.177) for 8120 reflections with ¦F _hkl¦ 4 ¦F _hkl¦. Rhombic system, space group Pbca, a = 18.0586(8), b = 19.9898(9), c = 20.5553(8) Å, V = 7420.2(6) ų. The structure is based on {(UO₂)₃[(S,Cr)O₄]₅}^4– anionic layers, formed by combination of UO₇ pentagonal bipyramids and TO₄ tetrahedra through common vertices. The { (UO₂)₃ [(S,Cr)O₄]₅}^4– layers are parallel to the (010) plane. The Cu²⁺ (H₂O)₆ octahedra and additional water molecules are located in the interplanar space and provide binding of the layers in the structure by hydrogen bonds. Based on the occupancy of tetrahedral positions, more accurate chemical formula of the compound should be written as Cu₂{(UO₂)₃[(S_0.804 Cr_0.196)O₄]₅} (H₂O)₁₇.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 408–411.Original Russian Text Copyright © 2004 by Krivovichev, Burns.     

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,crystal structure,and proton conductivity of KFe(H<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>2</Subscript>

KFe H₂P₂O7)₂ is synthesized at 443 K in molten polyphosphoric acids containing K and Fe ions, and its crystal structure is determined: triclinic unit cell with a = 4.9974(6) Å, b = 7.4766(9) Å, c = 7.8185(9) Å, = 82.29(2)°, = 83.37(2)° , = 74.13(2)° ; Z = 1, sp. gr. P . The structure is made up of infinite ribbons formed by corner-shared PO₄ tetrahedra and FeO₆ octahedra, with the K atoms in between. Neighboring ribbons are linked by hydrogen bonds. The proton conductivity of potassium iron(III) dihydrogen diphosphate is rather low.Translated from Neorganicheskie Materialy, Vol. 41, No. 1, 2005, pp. 74–77. Original Russian Text Copyright © 2005 by Chudinova, Murashova, Ilyukhin, Tarnopolskii, Yaroslavtsev.     

Synthesis and study of uranyl phosphates (UO<Subscript>2</Subscript>)<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>·<Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O

Uranyl phosphate (UO₂)₃(PO₄)₂·8H₂O was synthezied. Its dehydration was studied by X-ray diffraction, IR spectroscopy, and thermal and chemical analysis. The dehydration products were isolated and characterized by X-ray diffraction and IR spectroscopy. Their structural features were determined.     

Phase transitions and high-temperature crystal chemistry of polymorphous modifications of Cs<Subscript>2</Subscript>(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)

Phase transitions and thermal deformations of - and -Cs₂(UO₂)₂(MoO₄)₃ were studied by high-temperature X-ray diffraction analysis. In heating of -Cs₂(UO₂)₂(MoO₄)₃ to 625 ± 25°C, the reconstructive phase transition proceeds. -Cs₂(UO₂)₂(MoO₄)₃ is stable up to 700 ±25°C. The thermal expansion of both phases is sharply anisotropic: ₁₁ = 10 × 10^–6, ₂₂ = 33 × 10^–6, ₃₃ = 10 × 10^–6, _V = 53 × 10^–6 deg^–1 for -Cs(UO₂)₂(MoO₄)₃ and ₁₁ = 13 × 10^–6, ₃₃ = 3 × 10^–6, _V = 31 × 10^–6 deg^–1 for -Cs₂ (UO₂)₂ (MoO₄)₃. The anisotropy of thermal expansion is explained by features of the crystal structure of the compounds.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 405–407.Original Russian Text Copyright © 2004 by Nazarchuk, Krivovichev, Filatov.     

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.     

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.     

Graphite intercalation in the graphite-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-R (R = H<Subscript>2</Subscript>O,C<Subscript>2</Subscript>H<Subscript>5</Subscript>OH,C<Subscript>2</Subscript>H<Subscript>5</Subscript>COOH) systems

The electrochemical behavior of graphite in polar solvent-H₂SO₄ electrolytes is studied in a wide range of H₂SO₄ concentrations. The results demonstrate that, with decreasing H₂SO₄ concentration, the charging curves become smoother and shift to higher potentials, the stage index increases, and intercalation compounds are more difficult to obtain. At H₂SO₄ concentrations of 50% and lower, graphite polarization is accompanied by a significant overoxidation, as evidenced by the anomalously small intercalate layer thicknesses: 7.75–7.85 Å. Anodic polarization of graphite in electrolytes consisting of H₂SO₄ and a polar solvent (H₂O and C₂H₅OH) follows the same mechanism as in the case of the formation of graphite bisulfate. In going from water to C₂H₅OH, a less polar solvent, the intercalation threshold increases from 30 to 70% H₂SO₄. It is shown using a set of characterization techniques that, in the graphite-H₂SO₄-R (R = H₂O, C₂H₅OH) systems, the solvent is not intercalated into graphite. Stage I–III ternary graphite intercalation compounds (TGICs) are synthesized for the first time in the graphite-H₂SO₄-C₂H₅COOH system: stage I TGICs at H₂SO₄ concentrations above 70%, stage II in the range 30–70% H₂SO₄, and stage III at H₂SO₄ concentrations down to 10%. The intercalate layer thickness in the TGICs is 7.94 Å. The mechanism of TGIC formation in this system is shown to differ from those in mixtures of H₂SO₄ and other organic acids. Thermal analysis in combination with spectroscopic analysis of gaseous products provides clear evidence for intercalation of propionic acid into the TGIC and indicates that the thermal stability of this compound is lower than that of graphite bisulfate.Translated from Neorganicheskie Materialy, Vol. 41, No. 2, 2005, pp. 162–169.Original Russian Text Copyright © 2005 by Shornikova, Sorokina, Maksimova, Avdeev.     

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.     

Crystal structure of double acetates SrAnO<Subscript>2</Subscript>(OOCCH<Subscript>3</Subscript>)<Subscript>3</Subscript>·3H<Subscript>2</Subscript>O [An = Np(V), Pu(V)]

The crystal structure of isostructural Pu(V) and Np(V) acetates of the general composition SrAnO₂Ac₃ · 3H₂O (Ac = CH₃COO^?) was determined. The structures are based on complex anions [AnO₂Ac₃]^2? and Sr²⁺ cations combined into a three-dimensional framework with water molecules located in framework cavities. The An(V) atoms are characterized by the hexagonal-bipyramidal oxygen surrounding; the equatorial plane is formed by the O atoms of three acetate groups. The coordination surrounding of the Sr atom is a tetragonal antiprism formed by the O atoms of acetate ions and water molecules. The bond lengths within the coordination sphere decrease in passing from Np(V) to Pu(V): the average An=O and An-O bond lengths are 1.828(5) and 2.549(6) Å for Np and 1.811(4) and 2.530(4) Å for Pu, respectively.     

Low-Temperature Heat Capacities and Standard Molar Enthalpy of Formation of Potassium Benzoate C<Subscript>7</Subscript>H<Subscript>5</Subscript>O<Subscript>2</Subscript>K(s)

Potassium benzoate C₇H₅O₂K (CAS Registry No. 582-25-2) was synthesized by the method of liquid phase reaction. Chemical and elemental analyses, FTIR, and X-ray powder diffraction (XRD) techniques were applied to characterize the composition and structure of the compound. Low-temperature heat capacities of the compound were measured by a precision automated adiabatic calorimeter over the temperature range from 78 K to 398 K. A polynomial equation of the heat capacities as a function of temperature was fitted by the least-squares method. Smoothed heat capacities and thermodynamic functions of the compound were calculated based on the fitted polynomial. In accordance with Hess’s law, a reasonable thermochemical cycle was designed, and 100 mL of 1 mol · dm⁻³ NaOH solution was chosen as the calorimetric solvent. The standard molar enthalpies of dissolution for the reactants and products of the supposed reaction in the selected solvent were measured by an isoperibol solution-reaction calorimeter. Finally, the standard molar enthalpy of formation of the title compound C₇H₅O₂K (s) was derived to be -(610.94 ± 0.77) kJ · mol⁻¹.     

Etching behavior of CdTe in aqueous H<Subscript>2</Subscript>O<Subscript>2</Subscript>-HI-C<Subscript>6</Subscript>H<Subscript>8</Subscript>O<Subscript>7</Subscript> solutions

This paper examines the dissolution behavior of the (111)A, (111)B, (110), and (100) surfaces of CdTe single crystals in aqueous H₂O₂-HI-C₆H₈O₇ (citric acid) solutions. We have determined the dissolution rate of the crystals as a function of temperature and solution concentration, located the composition regions of polishing and selective etchants, and studied the microstructure and roughness of surfaces polished with optimized etchants. The etching behavior of CdTe is shown to depend on its crystallographic orientation.     

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.     

Synthesis and crystal structure CoNi<Subscript>2</Subscript>(BO<Subscript>3</Subscript>)<Subscript>2</Subscript>

A new metal orthoborate compound, cobalt dinickel orthoborate, CoNi₂(BO₃)₂ has been successfully synthesized for the first time. The title compound was synthesized by thermally-induced solid-state chemical reaction at 900°C between the initial reagents of Co(NO₃)₂ · 6H₂O, Ni(NO₃)₂ · 6H₂O and H₃BO₃ which were mixed with the mol ratio of 1: 2: 2 respectively. The obtained product was structurally characterized by X-ray powder diffraction technique. It has been found that the CoNi₂(BO₃)₂ crystallizes in the kotoite type and isostructural with the compounds having the chemical formula M₃(BO₃)₂ where M—Mg, Co and Ni. The synthesized compound belongs to the orthorhombic crystal system with the refined unit cell parameters of a = 5.419(9) Å, b = 8.352(0) Å, c = 4.478(8) Å and Z = 2. The space group was determined as Pnmn. Further characterizations by FTIR, elemental analysis and thermal analysis were also performed.     

Reactions of V<Subscript>2</Subscript>O<Subscript>5</Subscript>, Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>, and Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> with AlN

Reactions of vanadium, niobium, and tantalum pentoxides with aluminum nitride have been studied using X-ray diffraction. At temperatures from 1000 to 1600°C, we have identified various V, Nb, and Ta nitrides. The composition of the niobium and tantalum nitrides depends on the reaction temperature. The tendency toward nitride formation becomes stronger in the order V₂O₅ < Ta₂O₅ < Nb₂O₅.     

Photoluminescence and raman spectra of (Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>)<Subscript>0.95</Subscript>(Sm<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.05</Subscript> crystals

We have measured the photoluminescence and Raman spectra of (Ga₂S₃)_0.95(Sm₂O₃)_0.05 crystals and identified the mechanism of the energy transfer from the host to the rare-earth ion and the vibrational modes of the constituent atoms.     

Synthesis,crystal structure,and absorption spectra of a complex neptunium(v) chromate,Na<Subscript>3</Subscript>[NpO<Subscript>2</Subscript>(CrO<Subscript>4</Subscript>)<Subscript>2</Subscript>](H<Subscript>2</Subscript>O)<Subscript>5</Subscript>

A new Np(V) chromate complex with outer-sphere sodium cations, Na₃[NpO₂(CrO₄)₂](H₂O)₅ (I), was synthesized from aqueous solution. Its composition and structure were determined by single crystal X-ray diffraction. The structure of I is based on anionic chains of the composition [NpO₂(CrO4)2] _n ³ⁿ⁻, running along [010] and forming layers parallel to the (101) plane. The Na⁺ ions and water molecules of crystallization are arranged between the layers. The coordination polyhedra of the Np atoms (pentagonal bipyramids) are combined pairwise by sharing common equatorial edges formed by two bridging oxygen atoms of bidentate chelate-bridging CrO₄ groups. The absorption spectra of I in the IR and visible ranges are presented.