The crystal structures of Ba2LaRuO6 and Ca2LaRuO6

Neutron diffraction experiments have been performed to determine the structures of Ba₂LaRuO₆ and Ca₂LaRuO₆. Both are ordered, distorted perovskites. Ba₂LaRuO₆ is monoclinic, space group $\text{P}\text{2}{}_{\mathrm{<mtext>1</mtext>}}\text{n}$ with $\text{a}{}_0\text{=6.0285(7)}\text{A}\text{?}$, $\text{b}{}_0\text{=6.0430(7)}\text{A}\text{?}$, $\text{c}{}_0\text{=8.5409(6)}\text{A}\text{?}$, β=90.44(1)^o. The A sites are occupied by barium and the B sites by an ordered arrangement of lanthanum and ruthenium. Ca₂LaRuO₆ is triclinic, space group P1 with a₀=5.6179(5), b₀=5.8350(5), c⁰=8.0667(4), α=90.0^o, β=89.76(1)^o, γ=90.0^o. The A sites are occupied by calcium and lanthanum in a disordered manner, and the B sites are occupied by an ordered arrangement of calcium and ruthenium. The results reported in this paper thus contradict those of previous workers. The low-temperature magnetic structures are discussed briefly.     

Crystal data and thermal expansion of tricalciumborate

Single crystals of tricalciumborate were grown by the flux method. Ca₃B₂O₆ crystallizes in the rhombohedral system with the unit cell parameters $\text{a}{}_{\mathrm{R}}\text{= 6.3577(7)}\text{A}\text{?}$, α_R = 85.68(8)°, Z = 2. The equivalent hexagonal lattice parameters are a_H = 8.640(1), $\text{C}{}_{\mathrm{H}}\text{= 11.854(1)}\text{A}\text{?}$. The anisotropic thermal expansion parameters α_a = (1.00 ± 0.14) × 10^?5, α_c = (3.60 ± 0.47) × 10^?5 were determined by X-ray methods in the temperature interval 25 – 1000°C.     

Preparation and structure of EuIINb4O11

The occurrence of compound in the system has been studied by means of X-ray powder diffraction. A compound, Eu^IINb₄O₁₁, was found. The X-ray powder diffraction data for Eu^IINb₄O₁₁ could be indexed on a tetragonal cell with $\text{a}\text{=52.52}\text{A}\text{?}$, $\text{C}\text{=7.69}\text{A}\text{?}$. The temperature dependence of the magnetic susceptibility for this compound is expressed by the equation, $\text{X}{}_{\mathrm{M}}\text{=}\text{7.10}\text{(}\text{T}\text{+0.20)}$. This compound is oxidized at about 290°C or above in air.     

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.     

High pressure synthesis of Gd3InO6, Tb3InO6 and Lu3InO6

Three new compounds, X₃InO₆ (X = Gd, Tb, Lu) were prepared at 1–4 GPa, ～1050°C. They are monoclinic, space group $\text{P}\text{2}{}_1\text{n}$ with $\text{a}\text{? 8.9}\text{A}\text{?}$, $\text{b}\text{? 9.8}\text{A}\text{?}$, $\text{c}\text{? 5.9}\text{A}\text{?}$, β ～ 95° and Z = 4.     

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.     

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 $\text{“α}{}_{\mathrm{<mtext>c</mtext>}}\text{” = 5.246 ×10}{}^{\mathrm{?6}}\text{+ 6.369 ×10}{}^{\mathrm{?9}}\text{T}\text{? 7.480 ×10}{}^{\mathrm{?14}}\text{T}{}^2\text{/°}\text{C}$.     

The preparation and characterization of Ba3Te2O9; a new oxide structure

The structure of Ba₃Te₂O₉ has been determined from x-ray powder diffraction data and by profile refinement of neutron diffraction data. We find tellurium octahedrally coordinated as expected and the same face-shared [B₂O₉]^6? unit as observed in Ba₃W₂O₉. The phase Ba₃Te₂O₉ has, however, a Cs₃Fe₂F₉ type structure ($\text{P}\text{6}{}_3\text{mmc}$, $\text{a}\text{=}\text{5}\text{.8603(1)}\text{A}\text{?}$, $\text{c}\text{=14.3037(6)}\text{A}\text{?}$) rather than the Cs₃Tl₂Cl₉ structure (R3c) found for the tungsten analogue. The two oxide structures have the same BaO₃ layer sequence but differ only in the spatial arrangement of the [B₂O₉] groups in the lattice. Infrared and Raman spectra confirm the different site symmetries associated with the different packing of the tungstate and tellurate anions in their respective structures.     

Intercroissances des structures de type perovskite et SrO deficitaires en oxygene : Les oxydes Ln2−xSr1+xCu2O6−x/2 (Ln = Sm,Eu, Gd)

New oxides Ln_2?xSr_1+xO_6?x/2 (Ln = Sm, EU, GD), corresponding to oxygen deficient intergrowths of double perovskite and SrO layers have been isolated for 0.70 ≤ x ≤ 0.90. They are characterized by an orthorhombic cell, $\text{a}\text{?}\text{a}{}_{\mathrm{p}}\text{? 3.9}\text{A}\text{?}$, $\text{b}\text{?}\text{3a}{}_{\mathrm{p}}$, and $\text{c}\text{? 20}\text{A}\text{?}$. A structural model has been obtained, showing that this structure, although closely related to that of La_2?xSr_1+xCu₂O_6?x/2+δ exhibits a different distribution of the oxygen vacancies, involving for copper several coordinations. The semi-conductive properties of these compounds, very different from the semi-metallic behaviour of La_2?xSr_1+xCu₂O_6?x/2+δ is explained by the distribution of the oxygen vacancies in the structure.     

La liaison metal — metal dans les clusters M12O36: II — Preparation et etude structurale de la phase La3Ru3O11

La₃Ru₃O₁₁ was prepared either by oxidation of mixtures of $\text{3}\text{2}\text{La}{}_2\text{O}{}_3$: 3 Ru with KClO₃ at 900°C or by the oxidation of LaRuO₃ at 920°C with KClO₃, both in a gold boat introduced in a sealed silica tube. The crystal structure of this compound ($\text{a}\text{= 9.466(2)}\text{A}\text{?}\text{, S.G. Pn}\text{3,}\text{Z}\text{=4}$) has been solved by Fourier and least-squares methods to R = 0.022 (R_W = 0.031). As for the previously described Bi₃Ru₃O₁₁ and La₄Ru₆O₁₉, it contains ruthenium in formal oxidation state of 4.33; however, there is no longer metal - metal interaction, owing to the greater Ru - Ru distance (3.00 Å) and the closer approach of bridging oxygen (2.47 Å) within the dimeric unit Ru₂O₁₀. Therefore, this interaction is not a prerequisite for the formation and stability of the three-dimensional network Ru₁₂O₃₆.     

New phase with K2NiF4 structure in the LaLiFeO system

The existence has been proved, for the first time, in the LaLiFeO system of the phase (La_1.75Li_.25) (Fe_.5Li_.5)O_4?x with tetragonal symmetry ($\text{a}{}_{\mathrm{o}}\text{=3.765±0.001}\text{A}\text{?}$; $\text{c}{}_{\mathrm{o}}\text{=12.918±0.01}\text{A}\text{?}$; $\text{c}{}_{\mathrm{o}}\text{a}{}_{\mathrm{o}}\text{=3.43}$) and K₂NiF₄-type structure.This phase gives probably the first example of lithium distribution in both A and B sites of A₂BO₄-type mixed oxides. The high $\text{c}{}_{\mathrm{o}}\text{a}{}_{\mathrm{o}}$ ratio suggests a strong elongation of FeO₆ octahedra induced by a high spin Fe(IV) d⁴ configuration. The results of structural studies and of Mössbauer analysis, confirming the above conclusions, are reported.     

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 oxyde de rhenium en relation de structure avec V2O5

The authors describe a rhenium oxide, Re₂O₅. It was revealed and investigated by means of transmission electron microscopy and single diffraction. The orthorhombic unic cell is related to the ReO₃ cubic cell in terms of: b=c=a_c= 3,747 A and a= 2 $\text{a}{}_{\mathrm{c}}\text{√2= 10,598}\text{A}\text{?}$. The crystal structure is explained from patterns, according to the structural scheme of Me₂O₅ and particularly to vanadium pentoxide structure. It is obvious that there exists a close relationship between them.     

New tetrahedrally coordinated A2CdBr4 compounds (A = Cs,CH3NH3)

(CH₃NH₃)₂CdBr₄ and Cs₂CdBr₄ are two compounds with a tetrahedral CdBr₄-coordination. Their room temperature structures are determined. (CH₃NH₃)₂CdBr₄: monoclinic, $\text{P}\text{2}{}_1\text{c}$, $\text{a}\text{= 8.1227(13)}\text{A}\text{?}$, $\text{b}\text{= 13.4355(16)}\text{A}\text{?}$, $\text{c}\text{= 11.4194(13)}\text{A}\text{?}$, β = 96.194(11) °, z = 4. Cs₂CdBr₄: orthorhombic, Pnma, $\text{a}\text{= 10.235(5)}\text{A}\text{?}$, $\text{b}\text{= 7.946(3)}\text{A}\text{?}$, $\text{c}\text{= 13.977(5)}\text{A}\text{?}$, z = 4.     

Synthesis and characterization of europium(II)-holoborates,Eu2B5O9Cl and Eu2B5O9Br

Europium(II)-haloborates, Eu₂B₅O₉Cl and Eu₂B₅O₉Br, were synthesized and characterized by X-ray analysis, magnetic susceptibility and luminescent spectral measurements. The chloroborate Eu₂B₅O₉Cl crystallizes in the tetragonal system, D⁶₄-P4₂2₁2, with cell dimensions: a=11.349(4), $\text{c}\text{=6.500(4)}\text{A}\text{?}$ and Z=4, and Eu₂B₅O₉Br in the orthorhombic system, C¹⁰_2v-Pnn2 or D¹²_2h-Pnnm, with cell dimensions: a=11.503(3), b=11.382(3), $\text{c}\text{=6.484(2)}\text{A}\text{?}$ and Z=4. Both of them were paramagnets with paramagnetic Curie temperature at about ?1 K, and band emissions peaking at about 430 and 435 nm which were based on a 4f⁷-4f⁶5d transition of Eu²⁺ ion were observed on Eu₂B₅O₉Cl and Eu₂B₅O₉Br, respectively.     

An outline of the crystal-structure of Bi2Mo2O9

An outline of the structure of the catalyser component Bi₂Mo₂O₉ has been determined from X-ray powder diffractometer diagrams. The space group is $\text{P}{}^2\text{l}\text{n}$ ($\text{=}\text{P}{}^2\text{l}\text{c}$) with cell constants: $\text{a}\text{= 11.946 (2)}\text{A}\text{?}$, $\text{b}\text{= 10.795 (2)}\text{A}\text{?}$, $\text{c}\text{= 11.876 (2)}\text{A}\text{?}$ and β = 90.15 (2)°. There are eight formula units per cell. The positions of the metal-ions could directly be derived from the intensities of the strongest reflexions. With difference terms calculated from 19 strong reflexions a Δ F-synthesis was calculated, which revealed the approximate positions of the O^2?-ions. From packing considerations it was apparent that of 9 0^2?-ions one is only coordinated by Bi³⁺ and that Mo⁶⁺ must be tetrahedrally surrounded by 0^2?. These tetrahedra may be strongly distorted. The structure is not related to the scheelite-structure as has been assumed by some authors.     

The conversion from CrO2 into orthorhombic CrOOH

The reaction, $\text{2}\text{CrO}{}_2\text{+}\text{H}{}_2\text{O}\text{→ 2}\text{CrOOH}\text{+}\text{1}\text{2}\text{O}{}_2$, was confirmed to be a topotactic reaction by X-ray diffraction technique using a single crystal of CrO₂ as starting material. The crystallographic axial relation between CrO₂ and CrOOH was as follows: ^c(CrO₂^//c(CrOOH), ^a(CrO₂)^∧a(CrOOH)^{= a}(CrO₂)^∧b(CrOOH)^{= 1.7°}.     

On the pyrochlore type Ln2V2O7 (Ln: Rare-earth elements)

Pyrochlore type rare-earth vanadites (Ln₂V₂O₇) were prepared and some physical properties were investigated. Ln₂V₂O₇ (Ln:Tm, Yb or Lu) crystallized in the cubic space group $\text{O}{}_{\mathrm{<mtext>h</mtext>}}\text{=}\text{Fd}{}_3\text{m}\text{,}\text{a}{}_0\text{= 9.9575}\text{A}\text{?}\text{, 9.9346}\text{A}\text{?}\text{and}\text{9.9231}\text{A}\text{?}$ for Tm₂V₂O₇, Yb₂V₂O₇ and Lu₂V₂O₇, respectively. These compounds were all n-type semiconductors and paramagnets in the temperature range 90–300K.     

Refinement of the structure of K2Cr2O7

The parameters for the structure of K₂Cr₂O₇ have been refined from 7511 observed reflections; $\text{a}{}_{\mathrm{o}}\text{= 7.4200(6)}\text{A}\text{?}$, $\text{b}{}_{\mathrm{o}}\text{= 13.399(3)}\text{A}\text{?}$, $\text{c}{}_{\mathrm{o}}\text{= 7.3845(9)}\text{A}\text{?}$, cosα = ?0.1396(2) (α = 98°2'), cosβ = ?0.0154(2) (β = 90°53'), cosγ = ?0.1078(2) (γ = 96°11'). The discrepancy factor R(F_o²) = 0.0702 with a type 2 extinction correction. The average CrO distances are 1.609Å (unshared) and 1.783Å (shared).