Structure determination of (3D) P2NbS8

Tridimensional P₂NbS₈ crystallizes in P4?n2 tetragonal space group, with $\text{a}\text{= 12.0483(4)}\text{A}\text{?}$, $\text{c}\text{= 7.2070(5)}\text{A}\text{?}$, $\text{V}\text{= 1046.2(1)}\text{A}\text{?}{}^3$ and Z = 4. The structure was anisotropically refined down to R = 2.3% from 468 reflexions and 53 variables. It is built from [Nb₂S₁₂] biprismatic bicapped units (average $\text{d}{}_{\mathrm{Nb?S}}\text{= 2.571}\text{A}\text{?}$) made of S^?II and S^?II₂ anions (dianionic distance of 2.014(3) Å). The niobium atoms are found as isolated Nb^IV ? Nb^IV pairs ($\text{d}{}_{\mathrm{Nb?Nb}}\text{= 2.859(1)}\text{A}\text{?}$) in these niobium group otherwise linked to each other through (PS₄) tetrahedral units (average $\text{d}{}_{\mathrm{P?S}}\text{= 2.051}\text{A}\text{?}$) themselves constituting interbonded [P₄S₁₂] rings. The P₂NbS₈ three-dimensional network thus obtained is compared to the (2D) P₂NbS₈, layered phase already described.     

CuTa2O6 - crystal growth and characterization

The compound CuTa₂O₆ has been prepared as crystals from a Cu/O melt and found to be tetragonal ($\text{a}\text{= 7.510}\text{A}\text{?}$, $\text{c}\text{= 7.526}\text{A}\text{?}$) rather than cubic as reported in the literature. The coefficient of thermal expansion between room temperature and 1000°C was found to be 8.0 × 10^?6°C^?1. Electrical resistivity measurements on a crystal showed semiconductor behavior between room temperature ($\text{? = 2 × 10}{}^3\text{Ω}\text{cm}$) and 140°K ($\text{? = 7 × 10}{}^6\text{Ω}\text{cm}$) with an activation energy of E_A = 0.2 eV. Magnetic measurements between 4.2°K and room temperature showed Curie-Weiss behavior with a change in μeff at 120°K. For T>120°K, μeff = 1.76μ_B and θ_p = 0°K while for T<120°K μeff = 1.91 μB and θ_p = ?15°K.     

Thermal expansion of corundum structure Rh2O3

The directional thermal expansion coefficients of the corundum structure form of Rh₂O₃ were determined from room temperature to 850°C by x-ray diffraction methods. Rh₂O₃ has a lower thermal expansion and is less anisotropic in thermal expansion than alumina. The directional thermal expansion coefficients of Rh₂O₃ expressed in second degree polynominal form are: $\text{“α}{}_{\mathrm{<mtext>a</mtext>}}\text{” = 5.350 ×10}{}^{\mathrm{?6}}\text{+ 1.281 ×10}{}^{\mathrm{?9}}\text{T}\text{? 1.133 ×10}{}^{\mathrm{?14}}\text{T}{}^2\text{/°}\text{C}$ and $\text{“α}{}_{\mathrm{<mtext>c</mtext>}}\text{” = 5.246 ×10}{}^{\mathrm{?6}}\text{+ 6.369 ×10}{}^{\mathrm{?9}}\text{T}\text{? 7.480 ×10}{}^{\mathrm{?14}}\text{T}{}^2\text{/°}\text{C}$.     

Synthesis,structural and physical properties of the binary molybdenum chalcogenide phase Mo15Se19 and of the related compounds M2Mo15Se19 and M3Mo15Se19 (M=group 1A metal; Sn,Pb;Cd)

We present the synthesis, structure and physical properties of the binary phase Mo₁₅Se₁₉. This material was synthesized at low temperatures by oxidation of In₂Mo₁₅Se₁₉ or In₃Mo₁₅Se₁₉ by HCl gas. X-ray studies show that Mo₁₅Se₁₉ can exist in two crystallographic forms depending upon the indium phase used as starting material. Both phases contain large open channels and crystallize in a hexagonal unit cell with lattice parameters $\text{a}{}_{\mathrm{h}}\text{= 9.46}\text{A}\text{?}$ and $\text{c}{}_{\mathrm{h}}\text{= 19.61}\text{A}\text{?}$ when prepared from In₃Mo₁₅Se₁₉ (space group P6₃/m) and $\text{a}{}_{\mathrm{h}}\text{= 9.48}\text{A}\text{?}$ and $\text{c}{}_{\mathrm{h}}\text{= 58.76}\text{A}\text{?}$ when prepared from In₂Mo₁₅Se₁₉ (space group R3?c). The two structural forms of Mo₁₅Se₁₉ were found to be superconducting at 4.3K. The ease with which indium can be removed from the ternary compounds without disturbing the binary Mo-chalcogenide networks suggested that other metallic elements could be substituted for indium. In fact, several new M₂Mo₁₅Se₁₉ and M₃Mo₁₅Se₁₉ phases were synthesized, where M = group 1A element; Sn, Pb, and Cd. Several of their physical properties are also reported.     

Copper doped zinc oxide Y2BaZnO5: ERS and optical investigation

In copper doped Y₂BaZnO₅ oxides, copper exhibits a distorted square pyramidal coordination which is consistant with the values of g and A tensors obtained from O band ERS spectrum for a sample containing about 1 % Cu. Three values for g and A are observed, g₁ = 2.049₅, g₂ = 2.051₅, g₃ = 2.275, $\text{¦}\text{A}{}_1\text{¦ = 13 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$, $\text{¦}\text{A}{}_2\text{¦ = 10 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$ and $\text{¦}\text{A}{}_3\text{¦ = 147.5 10}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$. Since $\text{g}{}_1\text{?}\text{g}{}_2$ an approximate C_4v point symmetry can be assumed for copper. The electronic spectrum shows three bands at 11700, 14500 and 20500 cm^?1 which can be assigned to the transitions A₁ → B₁, B₂ → B₁ and E → B₁ respectively. The orbital reduction parameters are calculated and the bonding covalency is discussed.     

Determination de la structure cristalline de la variete a des hydroxycarbonates de terres rares LnOHCO3 (Ln = Na)

A probable model for the structure of the orthorhombic A - type neodymium hydroxycarbonate is presented. It relies on an optical determination of the site symmetry of OH^?, CO^2?₃, and Nd³⁺ atoms from infrared and visible absorption spectra, together with a computation of 50 X-ray diffraction lines intensities of a high resolution Guinier orthorhombic powder pattern ($\text{a}\text{= 4,953}\text{A}\text{?}$, $\text{b}\text{= 8,477}\text{A}\text{?}$, $\text{c}\text{= 7,210}\text{A}\text{?}$; space group Pmcn (n^o62)). The CO^2?₃ groups lies flat between mettalic planes as in the aragonite type of structure and are linked to OH^? by hydrogen bond ($\text{d(CO}{}^{\mathrm{2?}}{}_3\text{?}\text{OH}{}^{\mathrm{?}}\text{) = 2,52}\text{A}\text{?}$). The rare earth coordination is nine fold: two OH^? groups being closer (2,58 Å) than the seven oxygen from the CO^2?₃ groups (2,58 to 2,70 Å).     

Syntheses and magnetic properties of Eu3B2O6 and Sr3B2O6

Europium orthoborate and strontium orthoborate crystallize in the rhombohedral system with two formula units in a cell of dimensions $\text{a}{}_{\mathrm{R}}\text{=6.697}\text{A}\text{?}$, α_R=85.17° for Eu₃B₂O₆, and $\text{a}{}_{\mathrm{R}}\text{=6.695}\text{A}\text{?}$, α_R=85.00° for Sr₃B₂O₆. The equivalent hexagonal lattice parameters are $\text{a}{}_{\mathrm{H}}\text{=9.069}\text{A}\text{?}$, $\text{c}{}_{\mathrm{H}}\text{=12.542}\text{A}\text{?}$, and $\text{a}{}_{\mathrm{H}}\text{=9.046}\text{A}\text{?}$, $\text{c}{}_{\mathrm{H}}\text{=12.566}\text{A}\text{?}$ respectively. Eu₃B₂O₆ appears to be ferromagnetic below 7.5K.     

Sr2Mn2O5, an oxygen-defect perovskite with Mn(III) in square pyramidal coordination

An oxygen-defect perovskite Sr₂Mn₂O₅ was isolated by reduction of SrMnO_3?x perovskites in the presence of zirconium. Its structure, similar to that of Ca₂Mn₂O₅, has been determined by X-ray powder diffraction and HREM. The orthorhombic cell has the parameters : $\text{a}\text{= 5.523(1)}\text{A}\text{?}$, $\text{b}\text{= 10.761(5)}\text{A}\text{?}$, $\text{c}\text{= 3.811(1)}\text{A}\text{?}$. The possible space groups are Pbam and Pba2. The framework is built up from corner-sharing MnO₄ pyramids forming pseudo-hexagonal tunne$\text{l}$s running along 〈001〉 and perovskite tunnels running along 〈110〉 and 〈110〉. This oxide is antiferromagnetic with $\text{T}{}_{\mathrm{N}}\text{? 380 ± 10}\text{K}$ and $\text{θ}{}_{\mathrm{<mtext>P</mtext>}}\text{? 300 ± 10}\text{K}$.     

Alkaline earth scandates

In the CaOSrOSc₂O₃ and BaOSrOSc₂O₃ systems, complete series of mixed crystals were found for (Ca,Sr)Sc₂O₄ and (Sr,Ba)₃Sc₄O₉ respectively. In the BaOCaOSc₂O₃ system a new ternary phas?e with composition Ba_x(Ca_2xSc_2?2x)Sc₆O₁₂ was detected having an incommensurate structure which may be described with a basic hexagonal unit cell ($\text{a}\text{=9.7039}\text{A}\text{?}$, $\text{c}\text{=3.1274}\text{A}\text{?}$) and a second hexagonal cell having the same basic a-axis. The c-axis of the second cell is x-dependent: $\text{c}{}^{\mathrm{x}}\text{= 3.13/}\text{x}\text{A}\text{?}$, x varying from 0.782 to 0.736, corresponding to the region from BaCa₂Sc₈O₁₅ with $\text{c}{}^{\mathrm{x}}\text{= 4.00}\text{A}\text{?}$, to BaCa₂Sc₉O_16.5 with $\text{c}{}^{\mathrm{x}}\text{= 4.25}\text{A}\text{?}$.     

Structure cristalline de l'orthophosphate monoacide de cuivre monohydrate CuHPO4,H2O

Monophosphate hydrogen copper monohydrate : CuHPO₄,H₂O is monoclinic, space group $\text{P}\text{2}{}_1\text{a}$. The unit cell parameters are : a = 8.63(6), b = 6.35(3), $\text{c}\text{= 6.82(5)}\text{A}\text{?}$, β = 94.14(6°) and Z = 4. The crystal structure has been determined with 1249 independent reflexions and refined to a final R value of 2.9%. The crystal is built up of PO₄ tetrahedron and CuO₆ octahedron deformed by Jahn-Teller effect which are linked to form a three dimensional network.Based on the inter-ionic distances between Cu^II and O^2? in the recently determined structures of monoarsenates or phosphates, we give a value for the effective ionic radius of copper II.     

Concentration quenching of Tb3+ luminescence in LaOBr and Gd2O2S phosphors

The concentration quenching of trivalent terbium ${}^5\text{D}{}_{\mathrm{3,4}}\text{→}{}^7\text{F}{}_{\mathrm{J}}$ emissions from UV-excited (La, Tb) OBr and (Gd, Tb)₂O₂S phosphors was studied. The activation concentration x was varied from 5·10^?5 to 0.2 for (La_1?xTb_x) OBr and from 10^?3 to 0.1 for (Gd_1?xTb_x)₂O₂S. ${}^5\text{D}{}_3\text{→}{}^7\text{F}{}_{\mathrm{J}}$ emissions (blue) were observed to quench first and the Tb³⁺ concentration giving rise to maximum intensity was 0.003 in (La, Tb) OBr and between 0.005 and 0.01 in (Gd, Tb)₂O₂S. The optimum concentration for ${}^5\text{D}{}_4\text{→}{}^7\text{F}{}_{\mathrm{J}}$ (green) emissions was 0.05 in (La, Tb) OBr and 0.03 in (Gd, Tb)₂O₂S. Dipole-dipole and dipole-quadrupole interactions are possible mechanisms for the quenching of emissions from the ⁵D₃ and ⁵D₄ levels.A method for determining the Tb³⁺ concentration in these phosphors, based on the intensity ratios of the ${}^5\text{D}{}_3\text{→}{}^7\text{F}{}_{\mathrm{J}}$ and ${}^5\text{D}{}_4\text{→}{}^7\text{F}{}_{\mathrm{J}}$ transitions, is also presented.     

Stability of layered bismuth compounds in relation to the structural mismatch

The relation between the stability and the structural mismatch in layered bismuth compounds, (Bi₂O₂)²⁺(A_n?1B_nO_3n+1)^2?, was formulated on the basis of an elastic model. The pseudo-tetragonal lattice parameter, $\text{a}$, of layered bismuth compounds was estimated from the following equation,

$\text{a}\text{=}\text{[}\text{a}{}_{\mathrm{<mtext>B</mtext>}}\text{′}{}^2\text{ap}\text{′}{}^2\text{(nK+1)}\text{(}\text{ap}\text{′}{}^2\text{+}\text{a}{}_{\mathrm{<mtext>B</mtext>}}\text{′}{}^2\text{nK}\text{)]}$

$\text{1}\text{2}$

where a_B′ is the lattice parameter of the unconstrained Bi₂O₂ unit, a_P′ the lattice parameter of the unconstrained perovskite-like unit, n the number of perovskite like layer in one structural unit, and K a constant. The change of the strain energy for ionic substitutions was estimated from the elastic relationships. It was found that the increase of n in certain component systems causes the increase of the lattice parameter, $\text{a}$, and the increase of the strain energy. This provides an explanation for the existence of maximum of n. New compounds, Pb₃Bi₄Ti₆O₂₁ ($\text{a}\text{=5.476}$, $\text{b}\text{a}\text{=1.000}$ and $\text{c}\text{=58.1}\text{A}\text{?}$) and Pb₄Bi₄Ti₇O₂₄ ($\text{a}\text{=5.485}$, $\text{b}\text{a}\text{=1.000}$ and $\text{c}\text{=66.2}\text{A}\text{?}$) were described.     

Structure cristalline d'une nouvelle variete de pyrophosphate de nickel: Ni2P2O7

Three forms of nickel pyrophosphate are already known. A new form was prepared and structure determined by Patterson method. σ Ni₂P₂O₇ is monoclinic with a = 5.212(3), b = 9.913(5), $\text{c}\text{= 4.475(3)}\text{A}\text{?}$, β = 97°46(10). The space group is $\text{P}\text{2}{}_1\text{a}$. The structure was refined until a R value of 0.041 for 1374 independent reflexions. Framework is built with P₂O₇ groups and NiO₆ octaedra. The P-O-P bonding is linear. σ Ni₂P₂O₇ is isotypic with the pyrosilicate Er₂Si₂O₇.     

Un nouveau conducteur protonique [H(H2O)n]12Sb12O36 (n ⩽ 1)

Single crystals of K₁₄Sb₁₂O₃₆F₂ undergo rapid ion exchange in 9N sulfuric acid to produce “hydronium” compound (H(H₂O)_n)₁₂Sb₁₂O₃₆ (n ? 1). Between 30 and 140°C this phase undergoes a partial and reversible dehydratation in which approximately 85 % of its “H₃O⁺” content is converted to H⁺.The structures of hydrated and dehydrated phases have been refined by full-matrix least squares, respectively to factor R = 0.030 and 0.047. The conductivity of $\text{(H(H}{}_2\text{O)}{}_{\mathrm{<mtext>n</mtext>}}\text{)}{}_{12}\text{Sb}{}_{12}\text{O}{}_{36}\text{(σ}{}_{20}\text{? 1O}{}^7\text{Ω}{}^{\mathrm{?1}}\text{cm}{}^{\mathrm{?1}}$) increases in an Arrhenius relationship with an activation energy of 8.8 kcal.mole^?1, the dehydrated compound (H(H₂O)_0.33)₁₂Sb₁₂O₃₆ has a much lower conductivity but the same activation energy.     

The spinels CoRh2O4 and Co2RhO4

Polycrystalline CoRh₂O₄ and Co₂RhO₄ are cubic, spinel-type double oxides, S.G. Fd3m (No. 227), Z = 8. For CoRh₂O₄, $\text{a}\text{= 8.4992(1)}\text{A}\text{?}$, $\text{U = 613.95(3)}\text{A}\text{?}{}^3$, D_X = 7.11 Mgm^?3, $\text{x}\text{= 0.257}$, Co in 8(a) positions, R = 0.043. For Co₂RhO₄, $\text{a}\text{= 8.299(2)}\text{A}\text{?}$, $\text{U = 517.6(5)}\text{A}\text{?}{}^3$. D_X = 6.62 Mgm^?3, $\text{x}\text{= 0.261}$, half the Co content in 8(a) positions, R = 0.041. IR absorption band frequencies for both spinels are included.     

A series of rare earth silicates RE3+2M3+[SiO4]2 (OH)

A series of isotypic silicates of composition RE₂M[SiO₄]₂ (OH) with RE = La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, and M = Al³⁺, Fe³⁺ has been synthesized under hydrothermal conditions. Lattice constants of two members as determined from single crystal X-ray diffraction data are: La₂Al[SiO₄]₂ (OH) (La₂Fe[SiO₄]₂ (OH)) $\text{a}{}_{\mathrm{o}}\text{= 7.401 (7.346)}\text{A}\text{?}$, $\text{b}{}_{\mathrm{o}}\text{= 5.702 (5.862)}\text{A}\text{?}$, $\text{c}{}_{\mathrm{o}}\text{= 17.072 (97.196)}\text{A}\text{?}$, gb = 112.4 (112.5°), $\text{P}\text{2}{}_1\text{c}$, Z=4.     

A mixed valence compound in the two dimensional MPS3 family: V0.78PS3 structure and physical properties

The non stoichiometric compound V_0.78PS₃ has been obtained as single crystals from a preparation corresponding to the atomic ratio V/P/S = 1/1/3. It cristallizes with monoclinic symmetry, space group C2/m, with the unit cell parameters $\text{a}\text{= 5.867(1)}\text{A}\text{?}\text{,}\text{b}\text{= 10.160(2)}\text{A}\text{?}\text{,}\text{c}\text{= 6.657(1)}\text{A}\text{?}\text{, β = 107.08(2)°,}\text{V}\text{= 379.3(1)}\text{A}\text{?}{}^3$ and Z =4. The structure refinement was made down to a reliability factor value R = 3.3% from 445 reflexions (I > 3 σ (I)) and 31 variables. The material has same layer structure as FePS₃ with the occurrence of the thiophosphate anion (P₂S₆)^4?-including a P₂ pair. In V_0.78PS₃, the charge equilibrium implies the following developped formula : V_0.34^II V_0.44^III □_0.22 P^IV S₃^?II. The phase is a semi-conductor with a small activation energy of 0.24 eV, in accord with a vanadium mixed valence, and it presents, at low temperature, an antiferromagnetic order (T_N = 62 K).     

High pressure synthesis of orthorhombic SnO2

A dense form of SnO₂ with an orthorhombic structure has been synthesized at 158 kbar and 800 °C. The boundary separating the normal pressure phase (tetragonal SnO₂-I) from the high pressure phase (orthorhombic SnO₂-II) is represented by P(kbar) = 140.0 + 0.022 T(°C). The lattice parameters of the quenched high pressure phase (SnO₂-II) are : $\text{a}\text{= 4.714 ± 0.001}\text{A}\text{?}$, $\text{b}\text{= 5.727 ± 0.001}\text{A}\text{?}$ and $\text{c}\text{= 5.214 ± 0.001}\text{A}\text{?}$ with the cell volume $\text{V}\text{= 140.8 ± 0.1}\text{A}\text{?}{}^3$. The volume decrease for the transition is calculated to be 1.8 %.     

Crystal structure of KHSO4 · KH2PO4

KHSO₄ · KH₂PO₄ is monoclinic $\text{P}\text{2}{}_1\text{n}$ with Z = 2 and the following unit cell dimensions: a = 7.434(3); b = 7.341(3); $\text{c}\text{= 7.148(3)}\text{A}\text{?}$; β = 99.56(5)°.Crystal structure of this salt has been solved, using 1699 independent reflexions with a final R value: 0.034. PO₄ and SO₄ tetrahedra are randomly distributed in the arrangement with a resulting (P.S)-O mean distance of 1.508(3) Å.     

Crystal structure and magnetic properties of Cu4NiSi2S7

The structure of the compound Cu₄NiSi₂S₇ has been determined. It crystallizes in a new, monoclinic distorted sphalerite superlattice with the parameters: $\text{a}\text{= 11.551}\text{A}\text{?}$, $\text{b}\text{= 5.313}\text{A}\text{?}$, $\text{c}\text{= 8.165}\text{A}\text{?}$, β = 98.72°, $\text{V}\text{= 495.2}\text{A}\text{?}{}^3$, Z = 2, space group C2. The analogous compound Cu₄NiGe₂S₇ is isotypic. At a Neél temperature T_N = 20.2 K, Cu₄NiSi₂S₇ becomes antiferromagnetic. The magnetic moment of the paramagnetic phase is 2.6μ_B.