Crystal Structures and Magnetic Properties of 6H-Perovskites Ba3MRu2O9 (M=Y, In, La, Sm, Eu, and Lu)

Magnetic properties of quaternary oxides Ba₃MRu₂O₉ (M=Y, In, La, Sm, Eu, and Lu) are reported. Rietveld analyses of the X-ray diffraction data indicate that they adopt the 6H-perovskite structure and have the valence state of Ba₃M³⁺ Ru^4.5+₂O₉. All compounds are nonmetallic at least over the temperature range of 100-400 K. The magnetic susceptibilities show a broad maximum at 135-370 K except for the La compound, which shows a plateau around 22 K. In addition, another magnetic anomaly is observed at 4.5-12.5 K by the magnetic susceptibility and specific heat measurements for any compound. It is considered that this magnetic behavior is ascribed to the antiferromagnetic coupling between two Ru ions in a Ru₂O₉ dimer and to the magnetic interaction between the Ru₂O₉ dimers.     

Ba3WFe2O9 (P63mmc and Ba3WFe2O8.42(5) (Fm3m): Comparative study of the crystallographical and magnetic properties

Ba₃WFe₂O₉ has a hexagonal structure which belongs to space group $\text{P6}{}_3\text{mmc}$. Heated at 1350°C under a stream of helium, this compound gives an oxygen-deficient phase, the structure of which is ordered cubic (space group Fm3m). This passage from a hexagonal structure to a cubic structure is consistent with the decrease of the Goldschmidt tolerance factor resulting from the Fe³⁺ partial reduction. Ba₃WFe₂O_8.42(5) (cubic) was compared with Ba₃WFe₂O₉ (hexagonal) and Sr₃WFe₂O_8.85(3) (cubic) as to the crystallographical and magnetic properties. The study of the thermal stability in air for Ba₃WFe₂O_8.42(5) revealed a reoxidation in several steps and the existence of a new cubic compound, stable in air over a broad range of temperature, the formula of which may be written as Ba₃WFe₂O_8.71(5).     

Sm2O3Ga2O3 and Gd2O3Ga2O3 phase diagrams

Four definite compounds exist in the Sm₂O₃Ga₂O₃ binary phase diagram, namely: Sm₃GaO₆, Sm₄Ga₂O₉, SmGaO₃, and Sm₃Ga₅O₁₂. The $\text{3}\text{1}$ compound is orthorhombic (space group Pnna - Z.4) with the cell parameters: a = 11.40₀Å, b = 5.51₅Å, c = 9.07Å and belongs to the oxysel family. Sm₃GaO₆ and SmGaO₃ melt incongruently at 1715 and 1565°C; Sm₄Ga₂O₉ and Sm₃Ga₅O₁₂ have a congruent melting point at 1710 and 1655°C. With regard to the Gd₂O₃Ga₂O₃ system three definite compounds have been identified: Gd₃GaO₆, Gd₄Ga₂O₉, and Gd₃Ga₅O₁₂. Only the garnet melts congruently at 1740°C with the following composition: Gd_3.12Ga_4.88O₁₂. Gd₃GaO₆, and Gd₄Ga₂O₉ melt incongruently at 1760 and 1700°C. GdGaO₃ is only obtained by melt overheating which may yield an equilibrium or a metastable phase diagram.     

A pentagonal tunnel structure with copper in square planar coordination: The oxides KCuNb3O9 and KCuTa3O9

The structure of two new oxides KCuTa₃O₉ and KCuNb₃O₉ has been solved from X-ray powder data and by electron microscopy. Both compounds are orthorhombic, space group Pnc2 with $\text{a ? 8.8}$ Å, $\text{b ? 10.1}$ Å, and $\text{c ? 7.6}$ Å. Their host lattice is built up from corner-sharing MO₆ octahedra (M = Nb, Ta) forming pentagonal tunnels where the K⁺ ions are located. The copper ions are located in distorted perovskite CaCu₃Mn₄O₁₂-type cages and exhibit a square planar coordination. The relationships between these oxides and the TTB, HTB, ITB, and Ba_0.15WO₃ structures are discussed.     

Studies on magnetic susceptibility and specific heat for 6H-perovskite-type oxides Ba3LnIr2O9 (Ln=La, Nd, Sm-Yb)

Magnetic properties of the 6H-perovskite-type oxides Ba₃LnIr₂O₉ (Ln=La and Nd: monoclinic; Ln=Sm-Yb: hexagonal symmetry) were investigated. For all the title compounds, a specific heat anomaly was found at 5.3-17.4 K. At the corresponding temperatures, the magnetic susceptibilities show a slight variation in its gradient. These magnetic anomalies suggest the magnetic ordering of the magnetic moments (S=1/2) remaining in the Ir^4.5+₂O₉ face-shared bioctahedra. In addition, the Ln³⁺ ions show the onset of the antiferromagnetic ordering around these temperatures. The Ba₃NdIr₂O₉ only shows a ferromagnetic behavior below 17.4 K with a remnant magnetization of 1.25 μ_B. This behavior may be due to the ferromagnetic ordering of the Nd³⁺ moments.     

Magnetic behavior of tetrahedral Cr4+ compounds: Sr2CrO4, Ba2CrO4, and Ba3CrO5

The preparation of the compounds Sr₂CrO₄, Ba₂CrO₄, and Ba₃CrO₅ is described. The characterization of these three Cr⁴⁺ compounds by X-ray and magnetic susceptibility experiments has been conducted. The magnetic moments for Sr₂CrO₄, Ba₂CrO₄, and Ba₃CrO₅ were determined to be in good agreement with the calculated value expected for a tetrahedral Cr⁴⁺ ion. Weak antiferromagnetic ordering for all three compounds is indicated from the small paramagnetic Weiss constants determined from the susceptibility data in the temperature region 80–300 K. Distortions of the tetrahedra from ideality, as determined from the structural features, further cause a reduction in the magnetic moments from the theoretical values.     

Phase equilibrium relations in the binary systems LiPO3CeP3O9 and NaPO3CeP3O9

The LiPO₃CeP₃O₉ and NaPO₃CeP₃O₉ systems have been investigated for the first time by DTA, X-ray diffraction, and infrared spectroscopy. Each system forms a single 1:1 compound. LiCe(PO₃)₄ melts in a peritectic reaction at 980°C. NaCe(PO₃)₄ melts incongruently, too, at 865°C. These compounds have a monoclinic unit cell with the parameters: a = 16.415(6), b = 7,042(6), c = 9.772(7)Å; β = 126.03(5)°; Z = 4; space group $\text{C}{}_2\text{c}$ for LiCe (PO₃)₄; and a = 9.981(4), b = 13.129(6), c = 7.226(5) Å, β = 89.93(4)°, Z = 4, space group $\text{P2}{}_1\text{n}$ for NaCe(PO₃)₄. It is established that both compounds are mixed polyphosphates with chain structure of the type |M^I_IM^III_II (PO₃)₄|_∞M^I_I: alkali metal, M^III_II: rare earth.     

A structure, conductivity and dielectric properties investigation of A3CoNb2O9 (A=Ca, Sr, Ba) triple perovskites

The room temperature structures as well as the temperature-dependent conductivity and dielectric properties of the A₃CoNb₂O₉ (A=Ca²⁺, Sr²⁺ and Ba²⁺) triple perovskites have been carefully investigated. A constrained modulation wave approach to Rietveld structure refinement is used to determine their room temperature crystal structures. Correlations between these crystal structures and their physical properties are found. All three compounds undergo insulator to semiconductor phase transitions as a function of increasing temperature. The hexagonal Ba₃CoNb₂O₉ compound acts as an insulator at room temperature, while the monoclinic Ca₃CoNb₂O₉ compound is already a semiconductor at room temperature. The measured dielectric frequency characteristics of the A=Ba compound are excellent.     

Structural chemistry of Sr3Cr2WO9, Ca3Cr2WO9, and Ba3Cr2WO9

We have studied the preparation and crystallographic structure of three perovskite-type compounds: Sr₃Cr₂WO₉, cubic, the lattice parameter of which is a = 7.812Å; Ca₃Cr₂WO₉, tetragonal, the lattice parameters of which are a = 5.408 Å and c = 7.635Å; and Ba₃Cr₂WO₉, hexagonal, the lattice parameters of which are a = 5.691 Å and c = 13.957Å. We have compared these three structures and shown the relationship between the dimensions of the alkaline-earth metal and the existence of the different structures.     

Phase stability and ionic conductivity in substituted La2W2O9

Different substitutions, i.e. Sr²⁺, Ba²⁺, K⁺, Nb⁵⁺ and V⁵⁺, have been performed in the triclinic α-La₂W₂O₉ structure in order to stabilise the high temperature and better ionic conductor cubic β-phase. This approach has been used to try to obtain a new series of ionic conductors with LAMOX-type structure without molybdenum and presumably better redox stability compared to β-La₂Mo₂O₉. Nanocrystalline materials obtained by a freeze-drying precursor method at 600 °C exhibit mainly the β-La₂W₂O₉ structure, however, the triclinic α-form is stabilised as the firing temperature increases and the crystallite size grows. Only high levels of Ba²⁺ and V⁵⁺ substitutions retained the cubic form at room temperature after firing above 1100 °C. However, these phases are metastable above 700 °C, exhibiting an irreversible transformation to the low temperature triclinic α-phase. The synthesis, structure, phase stability, kinetic of phase transformation and electrical conductivity of these materials have been studied in the present report.     

Magnetic properties of barium uranate Ba2U2O7

Unique magnetic properties of a ternary uranate Ba₂U₂O₇ are reported. Magnetic susceptibility measurements reveal that this compound undergoes a magnetic transition at 19 K. Below this temperature, magnetic hysteresis was observed. The results of the low-temperature specific heat measurements below 30 K support the existence of the second-order magnetic transition at 19 K. Ba₂U₂O₇ undergoes a canted antiferromagnetic ordering at this temperature. The magnetic anomaly which sets in at 58 K may be due to the onset of one-dimensional magnetic correlations associated with the linear chains formed by U ions. The analysis of the experimental magnetic susceptibility data in the paramagnetic temperature region gives the effective magnetic moment μ_eff=0.73 μ_B, the Weiss constant θ=−10 K, and the temperature-independent paramagnetic susceptibility χ_TIP=0.14×10⁻³ emu/mole.The magnetic susceptibility results and the optical absorption spectrum were analyzed on the basis of an octahedral crystal field model. The energy levels of Ba₂U₂O₇ and the crystal field parameters were determined.     

Synthesis, structure and magnetic properties of the new mixed-valence vanadate Na2SrV3O9

The new complex oxide Na₂SrV₃O₉ was synthesized and investigated by means of X-ray diffraction, electron microscopy and magnetic susceptibility measurements. This oxide has a monoclinic unit cell with parameters a=5.416(1) Å, b=15.040(3) Å, c=10.051(2) Å, β=97.03(3)°, space group P2₁/c and Z=4. The crystal structure of Na₂SrV₃O₉, as determined from X-ray single-crystal data, is built up from isolated chains formed by square V⁴⁺O₅ pyramids. Neighboring pyramids are linked by two bridging V⁵⁺O₄ tetrahedra sharing a corner with each pyramid. The Na and Sr atoms are situated between the chains. Electron diffraction and HREM investigations confirmed the crystal structure. The temperature dependence of the susceptibility indicates low-dimensional magnetic behavior with a sizeable strength of the magnetic intra-chain exchange J of the order of 80 K, which is very likely due to superexchange through the two VO₄ tetrahedra linking the magnetic V⁴⁺ cations.     

Subsolidus phase relations in the BaTiO3TiO2 system

Ba₆Ti₁₇O₄₀, Ba₄Ti₁₃O₃₀, BaTi₄O₉, and Ba₂Ti₉O₂₀ are the only compounds which were found to have a stability range in the subsolidus of the BaTiO₃TiO₂ system. BaTi₂O₅ and BaTi₅O₁₁, reported in other studies, apparently are not stable. The compound reported as Ba₂Ti₅O₁₂ appears to have been mistaken for Ba₆Ti₁₇O₄₀. X-Ray diffraction powder data are given for this phase which is monoclinic with a = 9.890, b = 17.117, c = 18.933 Å and β=98°42.6′. The phase formulated previously as BaTi₃O₇ is shown to be Ba₄Ti₁₃O₃₀ based on structural and density considerations, phase equilibria, and single crystal and powder X-ray diffraction data. This compound is orthorhombic with a = 17.072, b = 9.862, and c = 14.059 Å, probable space group, Cmca. An idealized structure for this phase is proposed. Ba₂Ti₉O₂₀ decomposes above 1300°C in the solid state to BaTi₄O₉ plus rutile. Single crystals were grown using BaF₂ as a mineralizer.     

Structural and physical properties of 1:2 B-site-ordered perovskite Ba3CaIr2O9

The high-pressure phase of iridium-based compound Ba₃CaIr₂O₉ was synthesized using high-pressure sintering. Being different from the distorted hexagonal BaTiO₃ structure of the ambient Ba₃CaIr₂O₉, the high-pressure phase crystals into the 1:2 B-site-ordered perovskite structure with the space group P-3m1 (Z=1). Through fitting the X-ray powder diffraction (XRD) data with Rietveld analysis, in which the obtained R_p, R_wp, and R_exp factors are 7.49%, 11.4%, and 4.82%, respectively, the lattice parameters are a=5.8296(1) Å and c=7.1659(2) Å. The atomic coordinates and the main interatomic distances and bond angles were also obtained. The relationship of electrical resistivity versus temperature shows that the high-pressure phase of Ba₃CaIr₂O₉ is a semiconductor in the temperature range of 5-300 K. The measurement of temperature dependence of magnetic susceptibility indicates that it is paramagnetic.     

Preparation and comparison of the photoelectronic properties of Sr2Nb2O7 and Ba0.5Sr0.5Nb2O6

The two alkaline earth niobates Sr₂Nb₂O₇ and Ba_0.5Sr_0.5Nb₂O₆ have been prepared, their electronic properties measured, and their photoresponses compared. The indirect band gap in Sr₂Nb₂O₇ is 3.86 eV compared with 3.38 eV for Ba_0.5Sr_0.5Nb₂O₆. Hence, photoanodes composed of Sr₂Nb₂O₇ respond to much less of the “white” light spectrum than those made from Ba_0.5Sr_0.5Nb₂O₆. Nevertheless, their electrical outputs at an anode potential of 0.8 eV with respect to SCE in 0.2 M sodium acetate under “white” xenon arc irradiation of 1.25 W/cm² are comparable.     

Synthesis and crystal chemistry of BaNd2Ti3O10, BaNd2Ti5O14, and Nd4Ti9O24

Two new ternary compounds BaNd₂Ti₃O₁₀ (1:1:3) and BaNd₂Ti₅O₁₄ (1:1:5) have been identified in the BaONd₂O₃TiO₂ system. Single crystals of the compounds were grown and unit cell dimensions and space group symmetry were determined. BaNd₂Ti₃O₁₀ is orthorhombic with a = 3.8655 ± 0.0003, b = 28.156 ± 0.003 and c = 7.6221 ± 0.0007 Å and possible space groups are Cmcm or Cmc2. The compound melts congruently at 1640 ± 20°C. BaNd₂Ti₅O₁₄ is also orthorhombic with a = 22.346 ± 0.002, b = 12.201 ± 0.001 and c = 3.8404 ± 0.0003 Å and possible space groups are Pbam and Pba2. This compound melts congruently at 1540 ± 20°C. Single crystals of the binary compound Nd₄Ti₉O₂₄ were also grown and found to be orthorhombic with a = 35.289 ± 0.003, b = 13.991 ± 0.001, c = 14.479 ± 0.001 Å, space group Fddd.     

Crystal field effects on the magnetic behavior of Yb2V2O7 and Tm2V2O7

The bulk magnetic behaviors of the pyrochlores Yb₂V₂O₇ and Tm₂V₂O₇ were investigated. Calculated susceptibilities were adjusted to obtain the best fit to experimental data. A cubic crystal field Hamiltonian was used with B°₄ = ?0.633 and B°₆ = 0.000705 K for Yb³⁺ and B°₄ = 0.0297 and B°₆ = 0.000339 K for Tm³⁺. The calculated susceptibility for Yb³⁺ was found to be insensitive to the addition of an axial B°₂ parameter to the cubic Hamiltonian.     

Layered perovskite-related ruthenium oxychlorides: crystal structure of two new compounds Ba5Ru2Cl2O9 and Ba6Ru3Cl2O12

Single crystals of the title compounds were prepared using a BaCl₂ flux and investigated by X-ray diffraction methods using MoKα radiation and a charge coupled device (CCD) detector. The crystal structures of these two new compounds were solved and refined in the hexagonal symmetry with space group P6₃/mmc, a=5.851(1) Å, c=25.009(5) Å, ρ_cal=4.94 g cm⁻³, Z=2 to a final R₁=0.069 for 20 parameters with 312 reflections for Ba₅Ru₂Cl₂O₉ and space group , a=5.815(1) Å, c=14.915(3) Å, ρ_cal=5.28 g cm⁻³, Z=1 to a final R₁=0.039 for 24 parameters with 300 reflections for Ba₆Ru₃Cl₂O₁₂. The structure of Ba₅Ru₂Cl₂O₉ is formed by the periodic stacking along [001] of three hexagonal close-packed BaO₃ layers separated by a double layer of composition Ba₂Cl₂. The BaO₃ stacking creates binuclear face-sharing octahedra units Ru₂O₉ containing Ru(V). The structure of Ba₆Ru₃Cl₂O₁₂ is built up by the periodic stacking along [001] of four hexagonal close-packed BaO₃ layers separated by a double layer of composition Ba₂Cl₂. The ruthenium ions with a mean oxidation degree +4.67 occupy the octahedral interstices formed by the four layers hexagonal perovskite slab and then constitute isolated trinuclear Ru₃O₁₂ units. These two new oxychlorides belong to the family of compounds formulated as [Ba₂Cl₂][Ba_n+1Ru_nO_3n+3], where n represents the thickness of the octahedral string in hexagonal perovskite slabs.     

Non-centrosymmetric Ba3Ti3O6(BO3)2

The compound previously reported as Ba₂Ti₂B₂O₉ has been reformulated as Ba₃Ti₃B₂O₁₂, or Ba₃Ti₃O₆(BO₃)₂, a new barium titanium oxoborate. Small single crystals have been recovered from a melt with a composition of BaTiO₃:BaTiB₂O₆ (molar ratio) cooled between 1100°C and 850°C. The crystal structure has been determined by X-ray diffraction: hexagonal system, non-centrosymmetric space group, a=8.7377(11) Å, c=3.9147(8) Å, Z=1, wR(F²)=0.039 for 504 unique reflections. Ba₃Ti₃O₆(BO₃)₂ is isostructural with K₃Ta₃O₆(BO₃)₂. Preliminary measurements of nonlinear optical properties on microcrystalline samples show that the second harmonic generation efficiency of Ba₃Ti₃O₆(BO₃)₂ is equal to 95% of that of LiNbO₃.     

Determination des structures de deux ferrites mixtes nouveaux de formule BaLa2Fe2O7 et SrTb2Fe2O7

The structures of the two new ferrites BaLa₂Fe₂O₇ and SrTb₂Fe₂O₇ with tetragonal symmetry have been resolved by X-ray and neutron diffraction performed on powder samples. In both compounds the arrangement of atoms present a close resemblance with the idealized Sr₃Ti₂O₇ structure. It consists of a packing along the c axis of two different blocks. One is formed by the adjunction of two perovskite cells and the other one by a halved rocksalt Sr(Ba)O cell. The iron cation lattice is built by infinite double layers perpendicular to the c axis with the shortest Fe³⁺Fe³⁺ distances inside the double layers much shorter than between the layers. In BaLa₂Fe₂O₇, Ba²⁺ is located on a regular 12-coordinated site and La³⁺ in a regular 9-coordinated polyhedron. Fe³⁺ is surrounded by five oxygen neighbours at 1.98 Å, building a rather regular tetragonal pyramid, with a sixth oxygen at 2.25 Å. In SrTb₂Fe₂O₇, Sr has only eight close neighbours at ～2.80 Å and four more distant at 3.15 Å. Tb³⁺ has seven close neighbours, six building a distorted octahedron with the largest triangular face capped by the seventh oxygen. Fe³⁺ again has five neighbours, but due to the lowering of the symmetry, the square pyramid has become a distorted trigonal bipyramid.