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.     

Contribution a l'etude des proprietes magnetiques du dichlorure de vanadium VCl2

The magnetic properties of VCl₂ have been interpreted on the basis of a G.S. Rushbrooke et P.J. Wood model for Heisenberg bidimensional interactions. The calculation of the exchange integral leads to a value of $\text{J}\text{k}{}_{\mathrm{b}}$ close to ? 22,5 K. The strong antiferromagnetic intraplanar V – V interactions seem to result from direct t_2g - t_2g coupling.     

ESR evidence for the existence of rutile-type,nonstoichiometric vanadium antimonate

A nonstoichiometric vanadium antimonate has been synthesized from a high temperature solid state reaction of V₂O₅ and Sb₂O₃. Powder-X-ray diffraction data of this phase could be indexed on a tetragonal basis with $\text{a}\text{= 4.60}\text{A}\text{?}$, $\text{c}\text{= 3.02}\text{A}\text{?}$. The phase exhibits a well resolved hyperfine ESR spectrum at 298 K due to V(4+)(3d′) ions interacting with ${}^{51}\text{V}\text{(}\text{I}\text{=}\text{7}\text{2}\text{)}$, thus establishing its identity as a rutile type phase postulated earlier. The ESR parameters are $\text{g}{}_{\mathrm{}}\text{= 1.933±0.002}$, g_⊥ = 1.984±0.002, $\text{A}{}_{\mathrm{}}\text{= 193±3}\text{G}$, A_⊥ = 75±3G. Present results are discussed in relation to ESR of V(4+) in other rutile-type hosts.     

Une modelisation du comportement magnetique d'un compose de l'iridium pentavalent: LaLi12Ir12O3

A new interpretation is proposed for the magnetic properties of perovskite-type iridium (+V) oxide $\text{LaLi}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{Ir}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{O}{}_3$. In its unusual +5 oxidation state iridium has a t⁴_2ge⁰_g configuration. The magnetic susceptibility has been calculated assuming cubic symmetry of the crystal field and a Coulomb repulsion of the same order of magnitude than spin-orbit coupling. Fitting of the experimental data leads to a single spin-orbit constant $\text{ζ ? 3470}\text{cm}{}^{\mathrm{?1}}$ close to that of previously investigated Ir(+V) compounds.     

Crystal structures and crystal chemistry in the system Na1+xZr2SixP3−xO12

As part of a search for skeleton structures for fast alkali-ion transport, the system Na_1+xZr₂Si_xP_3?xO₁₂ has been prepared, analyzed structurally and ion exchanged reversibly with Li⁺, Ag⁺, and K⁺ ions. Single-crystal x-ray analysis was used to identify the composition NaZr₂P₃O₁₂ and to refine its structure, which has rhombohedral space group R3?c with cell parameters $\text{a}{}_{\mathrm{<mtext>r</mtext>}}\text{= 8.815(1)}\text{A}\text{?}$ and $\text{c}{}_{\mathrm{<mtext>r</mtext>}}\text{= 22.746(7)}\text{A}\text{?}$. A small distortion to monoclinic symmetry occurs in the interval 1.8 ≤x≤ 2.2. The structure for Na₃Zr₂Si₂PO₁₂, proposed from powder data, has space group $\text{C}\text{2}\text{c}$ with $\text{a}{}_{\mathrm{<mtext>m</mtext>}}\text{= 15.586(9)}\text{A}\text{?}$, $\text{b}{}_{\mathrm{<mtext>m</mtext>}}\text{= 9.029(4)}\text{A}\text{?}$, $\text{c}{}_{\mathrm{<mtext>m</mtext>}}\text{= 9.205(5)}\text{A}\text{?}$, and β = 123.70(5)° Both structures contain a rigid, three-dimensional network of PO₄ or (SiO₄) tetrahedra sharing corners with ZrO₆ octahedra and a three-dimensionally linked interstitial space. Of the two distinguishable alkali-ion sites in the rhombohedral structure, one is completely occupied in both end members, the occupancy of the other varies across the system from 0 to 100 percent. Several properties are compared with the fast Na⁺-ion conductor β-alumina.     

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.     

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.     

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).     

Strontium metaniobate: Its crystallography,polymorphism, and isomerism

Three polymorphic forms of SrNb₂O₆ are recognized. The monoclinic form has been prepared and studied by x-ray powder diffraction techniques and differential thermal analysis. The results of this study show that SrNb₂O₆ crystallizes in a pseudo-orthorhombic unit cell with $\text{a}{}_{\mathrm{o}}\text{= 10.99}\text{A}\text{?}$, $\text{b}{}_{\mathrm{o}}\text{= 7.70}\text{A}\text{?}$ and $\text{c}{}_{\mathrm{o}}\text{= 5.66}\text{A}\text{?}$. Its crystal chemical relations to the other meta-niobates and its thermodynamic stability are discussed.     

Macle et structure cristalline de Mn0,75Ga2,17S4

Twins of $\text{Mn}{}_{\mathrm{<mtext>1?</mtext><mtext>x</mtext>}}\text{Ga}{}_{\mathrm{<mtext>2+</mtext><mtext>2</mtext><mtext>3</mtext><mtext>x</mtext>}}\text{S}{}_4$ were used for crystal structure determination. Twinning is explained by a reticular pseudomerihedry. Axis, plane and obliquity of the twin have been determined. Cell dimensions are: $\text{a = b}\text{= 5.456(2)}\text{A}\text{?}$; $\text{c}\text{= 10.220(4)}\text{A}\text{?}$; α = β = γ = 90°; space group 14; Z = 2. The final R value is 0.059. The material is isostructural with CdGa₂S₄.     

On a new structural type of fluorine compounds : Crystal and magnetic structures of a high pressure form of PdF2

A new structural type of MF₂ fluorine compounds has been studied using neutron diffraction. The structure of the high pressure form of Pd difluoride has been shown to derive from the fluorite type by a rhombohedral distortion of the cubic environment of the cations. The coordination number of the cations is VI + II : the six nearest neighbor fluorine atoms form a distorted octahedron with $\text{M}\text{?}\text{F}{}_1\text{? 2.18}\text{A}\text{?}$, while two further anions correspond to $\text{M}\text{?}\text{F}{}_2\text{? 3.17}\text{A}\text{?}$. Distances and angles have been compared with those of other Pd compounds. The structure of the high pressure form of PdF₂ has been refined via neutron diffraction ($\text{a}\text{= 5.329}\text{A}\text{?}$, space group Pa3 or P2₁3). This phase orders antiferromagnetically below 190 ± 5 K and the magnetic structure has been determined on the basis of both collinear and noncollinear models. The magnetic data have been compared with results obtained for other d⁸ or d⁹ difluorides.     

Synthese et caracterisation du pentafluorotellurate (IV) de sodium NaTeF5

Sodium pentafluorotellurate (IV) NaTeF₅ has been prepared by slow evaporation of a $\text{1}\text{1}$ mixture of sodium fluoride and tellurium dioxyde in 50 % aqueous hydrofluoric acid.NaTeF₅ has an orthorhombic structure, parameters of which are $\text{a}\text{= 9.10}{}_5\text{A}\text{?}$$\text{b}\text{= 11.30}{}_6\text{A}\text{?}$$\text{c}\text{= 10.12}\text{A}\text{?}$     

The absolute configuration of RbClO3

The positional parameters of the structure of RbClO₃ have been determined from 171 x-ray reflections; $\text{a}{}_{\mathrm{<mtext>no</mtext>}}\text{= 6.092(1)}\text{A}\text{?}$$\text{c}{}_{\mathrm{<mtext>o</mtext>}}\text{= 8.173(2)}\text{A}\text{?}\text{, ?}\text{cal}\text{= 3.203}\text{g/cc}{}^3\text{and S.G.}\text{=}\text{R}\text{3}\text{m}$. The absolute configuration of the structure was determined by a least-squares adjustment of the complex anomalous dispersion of Rb and Cl. The ClO distances are 1.478(5)Å and the RbO distances are 3.530(8)Å.     

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.     

Growth and some properties of barium-cadmium formate single crystals: (II) X-ray and infrared studies

An analysis of the powder pattern of BaCd(HCO₂)₄ ·2H₂O shows that the structure belongs to space group p $\text{2}{}_1\text{c}$$\text{a}\text{= 11.907 (4)}\text{A}\text{?}$, $\text{b}\text{= 13.204(4)}\text{A}\text{?}$, $\text{c}\text{= 13.823(3)}\text{A}\text{?}$, β = 31.188(9)° with four molecules per unit cell. The infrared spectra of polycrystalline barium-cadmium formate has been measured in the region 650–4600 cm^?1. The influence of metal ion on carboxylate stretching frequencies of formate ion is investigated and the possible correlations between spectra and structure considered.     

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.     

Ordering of interstitial nitrogen and oxygen in vanadium near to V8N and V8O

The ordered structure of the V₈N subnitride was studied by X-rays, electron diffraction and electron microscopy. V₈N exists in two different modifications (α′ and α″). The vanadium sublattice of both phases is pseudo-tetragonal, in reality triclinic, with lattice parameters: $\text{α}{}_{\mathrm{<mtext>o</mtext>}}\text{=}\text{b}{}_{\mathrm{o}}\text{= 3.114}\text{A}\text{?}$, $\text{c}{}_{\mathrm{o}}\text{= 2.994}\text{A}\text{?}$, α_o = β_o = 90.5^o ± 0.1^o, γ_o = 90^o. The proposed unit cell of α′-V₈N has dimensions: a = 2√2 a_o, c = 2c_o and corresponds to V₃₂N₄. Doublets of nitrogen atoms occupy two sets of octahedral cavities whose shortest axes are aligned along the x and y directions of the sublattice in an ordered fashion. The α″-V₈N phase is a periodically twinned modification of the α′-V₈N, the twin plane being of the (001) type. The V₈O suboxide has the same structure as the α″-V₈N, the sublattice parameters being: $\text{a}{}_{\mathrm{o}}\text{=}\text{b}{}_{\mathrm{o}}\text{= 3.11}\text{A}\text{?}$, $\text{c}{}_{\mathrm{o}}\text{= 2.994}\text{A}\text{?}$, α_o = β_o = 90.3^o ± 0.1^o, γ_o = 90^o.     

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).     

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.     

TlxTi6Se8 and TlxNb6Se8, two phases with filled up Nb3Te4 type of structure showing pronounced cation disorder

The new ternary chalcogenides Tl_xTi₆Se₈ (x= 0.76) and Tl_xNb₆Se₈ (x= 0.70) crystallize with a partially filled up Nb₃Te₄-structure: space group $\text{P}\text{6}{}_3\text{m}$, z= 1 with

$\text{a= 9.882(1) c= 3.590(1)}\text{A}\text{?}\text{(Tl}{}_{0.76}\text{Ti}{}_6\text{Se}{}_8\text{)}$

$\text{a= 10.033(2) c= 3.475(1)}\text{A}\text{?}\text{(Tl}{}_{0.70}\text{TNb}{}_6\text{Se}{}_8\text{)}$

The crystal structures were determined from single crystal diffractometer data and refined to a conventional R-value of 0.077 and 0.055 respectively. The T1 atoms in the octahedral channels cannot be localized. In Tl_xTi₆Se₈ diffuse scattering indicates one-dimensional short range order. A model of the cation distribution in Tl_0.76Ti₆Se₈ is discussed.