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.     

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.     

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 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.     

Effect of complexation on crystallization of plutonium(IV) oxalate in the system Pu(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>-HNO<Subscript>3</Subscript>-H<Subscript>2</Subscript>C<Subscript>2</Subscript>O<Subscript>4</Subscript>

The published data on complexation in the system Pu(NO₃)₄-HNO₃-H₂C₂O₄ were treated on the basis of a unified approach to determination of the oxalate ion concentration. Because of discrepancies between results published by different researchers, additional experiments on crystallization of Pu(IV) oxalate were carried out at widely varied excess and deficiency of oxalic acid. These experiments confirmed high stability of the complex cations PuC₂O ₄ ²⁺ . The upper boundary of the field of metastable supersaturated solutions of Pu oxalate at the initial Pu concentration of 15–50 g l^?1 was determined.     

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.     

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.     

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.     

Low-loss,high-purity (TeO<Subscript>2</Subscript>)<Subscript>0.75</Subscript>(WO<Subscript>3</Subscript>)<Subscript>0.25</Subscript> glass

By melting a mixture of high-purity oxides in a platinum crucible under flowing purified oxygen, we have prepared (TeO₂)_0.75(WO₃)_0.25 glass with a total content of 3d transition metals (Fe, Ni, Co, Cu, Mn, Cr, and V) within 0.4 ppm by weight, a concentration of scattering centers larger than 300 nm in size below 10² cm⁻³, and an absorption coefficient for OH groups (λ ∼ 3 μm) of 0.008 cm⁻¹. The absorption loss in the glass has been determined to be 115 dB/km at λ = 1.06 μm, 86 dB/km at λ = 1.56 μm, and 100 dB/km at λ = 1.97 μm. From reported specific absorptions of impurities in fluorozirconate glasses and the impurity composition of the glass studied here, the absorption loss at λ ∼ 2 μm has been estimated at ≤100 dB/km. The glass has been drawn into a glass-polymer fiber, and the optical loss spectrum of the fiber has been measured.     

Oxidation of Pu(IV) to Pu(VI) with an XeO<Subscript>3</Subscript> + H<Subscript>2</Subscript>O<Subscript>2</Subscript> Mixture in a Perchloric Acid Solution

In a perchloric acid solution, XeO₃ does not oxidize Pu(IV), but the addition of H₂O₂ leads to the accumulation of Pu(VI). It is assumed that Pu(IV) forms a complex with XeO₃. The reaction of the complex with hydrogen peroxide generates OH radicals, which oxidize Pu(IV) to Pu(V). The latter disproportionates to Pu(IV) and Pu(VI).     

Liquid-phase epitaxy of NdAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and Yb-doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Epitaxial layers of NaAl₃(BO₃)₄ (NAB) and YAl₃(BO₃)₄〈Yb〉 (YAB〈Yb〉) containing up to 10 at % Yb have been grown by liquid-phase epitaxy on YAB substrates. Their growth kinetics have been studied at relative supersaturations of the high-temperature solution from 2 × 10^?2 to 16 × 10^?2. The ytterbium concentration in YAB〈Yb〉 has been shown to vary little during the epitaxial process. Near the edges of the substrate, the surface morphology of the layers is complicated by vicinals, which have a spiral form in the case of YAB〈Yb〉. On \(\{ 10\overline 1 1\} \) YAB substrates, homogeneous single-crystal NAB films have been grown.     

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.     

Phonons in mixed superionic fluorites (BaF<Subscript>2</Subscript>)<Subscript>1-x</Subscript>(LaF<Subscript>3</Subscript>)<Subscript>x</Subscript>

In recent years, the fluorite-structured solid solutions with the general formula, (MF₂)_1-x(RF₃)_x (M = Ca, Sr, Ba, Pb and R is a rare-earth element or Y), have been the subject of numerous experimental studies focussed on their superionic properties. The overall cubic crystal symmetry (space group Fm3m) is conserved up to x ≶ x_max, where x_max ⊁ 0.4-0.5 depending on M and R. The zone centre phonons and phonon dispersion along three symmetry directions of the mixed superionic compound (BaF₂)_1-x(LaF₃)_x have been investigated by applying de Launey angular force model for x ≶ x_max. The calculated results are compared and explained with available experimental results.     

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.     

Electrical Conductivity and Viscosity of 1-Hexyl-3-methylimidazolium Bis(trifluorosulfonyl)imide, [C<Subscript>6</Subscript>mim] [(CF<Subscript>3</Subscript>SO<Subscript>2</Subscript>)<Subscript>2</Subscript>N] (CAS-RN# 382150-50-7)

The electrical conductivity and viscosity of 1-hexyl-3-methylimidazolium bis(trifluorosulfonyl)imide, [C₆mim] [(CF₃SO₂)₂N], were measured at atmospheric pressure, between 270 K and 350 K, for samples with an amount of water not exceeding 200 ppm, as part of International Union of Pure and Applied Chemistry Project 2002-005-1-100. Water content was monitored before and after measurements, by coulometric Karl–Fisher titration. Special care was taken with ionic liquid manipulation in view of the measurement uncertainty budget. The uncertainties of the electrical conductivity measurements and of the viscosity measurements are estimated to be better than 2.0 % and 0.5 %, respectively. Results were compared with data from other authors, and all data were correlated as a function of temperature.     

Specific absorption coefficient of chromium in (TeO<Subscript>2</Subscript>)<Subscript>0.80</Subscript>(MoO<Subscript>3</Subscript>)<Subscript>0.20</Subscript> glass

We have prepared (TeO₂)_0.80(MoO₃)_0.20 glass samples containing 0.01 to 0.11 wt % chromium and determined their optical transmission in the range from 450 to 2800 nm. The glasses have been shown to have a strong absorption band centered at 660 nm. From the attenuation coefficient as a function of Cr³⁺ concentration in the glasses, we have evaluated their specific absorption coefficient, which has been shown to be 190 ± 2 cm^–1/wt % at the maximum of the absorption band.     

Beta-LaSc<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>: correction of the crystal structure

The published structure data of trigonal beta-LaSc₃(BO₃)₄ are incorrect because they are not compatible with the formula of the compound. After correcting the positional atom co-ordinates of one O atom the structure is found to be isotypic with CeSc₃(BO₃)₄ which crystallizes with the huntite CaMg₃(CO₃)₄ structure type.Response to paper, titled "Structure of medium temperature phase -LaSc₃(BO₃)₄ crystal," by He MY et al., published in MRI, vol. 2, issue 6, pp. 345–348, DOI     

Dielectric properties of Be(IO<Subscript>3</Subscript>)<Subscript>2</Subscript>⋅4H<Subscript>2</Subscript>O crystals

The article studies the dielectric properties, dc conductivity and ac conductivity of Be(IO₃)₂⋅4H₂O single crystals. The dielectric constant ε has been defined for the three directions of the vectors a, b and c in the crystals in the temperature interval 280–340 K and frequency range 100 Hz–10⁶ Hz. The crystals show strongly expressed anisotropy, at 20 ^∘C and frequency 100 Hz ε_a = 235, ε_b = 30 and ε_c = 85. The frequency dependence of ε is evidence of the presence of low-frequency relaxation polarization in the crystals. The activation energies of the three directions in the crystals have been derived from the temperature dependence of dc conductivity, and they are 1.03 eV, 0.836 eV and 1.2 eV respectively.     

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 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.