New lead vanadium phosphate with langbeinite-type structure: Pb1.5V2(PO4)3

The new lead vanadium phosphate Pb_1.5V₂(PO₄)₃ was synthesized by solid state reaction and characterized by X-ray powder diffraction, electron microscopy, and magnetic susceptibility measurements. The crystal structure of Pb_1.5V₂(PO₄)₃ (a = 9.78182(8) Å, S.G. P2₁3, Z = 4) was determined from X-ray powder diffraction data and belongs to the langbeinite-type structures. It is formed by corner-linked V³⁺O₆ octahedra and tetrahedral phosphate groups resulting in a three-dimensional framework. The lead atoms are situated in the structure interstices and only partially occupy their positions. An electron microscopy study confirmed the structure solution. Magnetic susceptibility measurements revealed Curie-Weiss (CW) behavior for Pb_1.5V₂(PO₄)₃ at high temperature whereas at around 14 K an abrupt increase on the susceptibility was observed.     

Crystal growth and structure determinations of potassium hafnates: K2Hf2O5 and K4Hf5O12

Crystals of K₂Hf₂O₅ and K₄Hf₅O₁₂ were grown from molten potassium hydroxide flux. The crystal structures were determined by single-crystal X-ray diffraction. K₂Hf₂O₅ crystallizes in the space group Pnna of the orthorhombic system, with unit cell dimensions of a = 5.780(1) Å, b = 10.640(2) Å, and c = 8.666(2) Å. This compound contains infinite chains of HfO₆ octahedra that form a channel structure. K₄Hf₅O₁₂ crystallizes in the space group of the trigonal system, with unit cell dimensions of a = 5.7877(2) Å and c = 10.3693(7) Å. This compound possesses a layered structure with six-coordinate Hf in three different coordination environments (trigonal prismatic, distorted octahedral, and regular octahedral).     

Crystal structures of KBa2Nb5O15 and LaK2Nb5O15 with the TTB-type structure

Single crystals of two niobates, KBa₂Nb₅O₁₅ and LaK₂Nb₅O₁₅, were synthesized by high-temperature reaction and the crystal structures were determined by single crystal X-ray diffraction data. Although the space groups for these compounds were different (the non-centrosymmetrical space group P4bm (#100) for KBa₂Nb₅O₁₅ and the centrosymmetrical one P4/mbm (#127) for LaK₂Nb₅O₁₅), both compounds had the same tetragonal tungsten bronze-type (hereafter TTB-type) structure. The lattice parameters and R-factors of KBa₂Nb₅O₁₅ (LaK₂Nb₅O₁₅) were a = 12.533(2) (12.563(2)) and c = 4.0074(9) (3.9179(9)) Å, and R₁ = 0.040 (0.047) and wR₂=0.131 (0.120), respectively. From the crystal structural analysis, it was clarified that distribution of two large cations was different from each other in the way that K and Ba atoms in KBa₂Nb₅O₁₅ were distributed statistically at two crystallographic sites and K and La atoms in LaK₂Nb₅O₁₅ were ordered.     

Synthesis of single-phase Sr3Co2Fe24O41 Z-type ferrite by polymerizable complex method

Synthesis of single-phase Sr₃Co₂Fe₂₄O₄₁ Z-type (Sr₃Co₂Z) ferrite was realized by adopting the polymerizable complex method. Crystal structure of samples has been investigated by powder X-ray diffraction (XRD). Single-phase Sr₃Co₂Z ferrite was obtained by heating at 1473 K for 5 h in air. Magnetic properties were discussed by measurements of M-H curves with vibrating sample magnetometer (VSM). Sr₃Co₂Z ferrite prepared by polymerizable complex method showed typical M-H curve of soft ferrite, with a saturation magnetization of 21.5μ_B/formula unit (50.5 emu/g) and a coercive force of 0.014 T at room temperature.     

Preparation and crystal structure of a new cesium iron niobium oxide: Cs3Fe0.44Nb5.56O16

Single crystals of a new niobium oxide, Cs₃Fe_0.44Nb_5.56O₁₆ were prepared at 1200°C under an Ar atmosphere. This compound has the orthorhombic space group Pbcm and Z=4. The lattice parameters were a=10.470(3), b=7.514(4) and c=21.312(3) Å, and the final R-factors were R=0.027 and R_w=0.033 for 1085 unique reflections. The crystal structure is a three-dimensional tunnel structure built up by edge- and corner-sharing NbO₆ octahedra and (Fe,Nb)O₄ tetrahedra and cesium atoms are located in two types of tunnels. The Cs⁺ ion in the tunnels was ion-exchanged partially with Rb⁺ ion.     

Crystal structures of CdTi2O4(OH)2 and LaTiSbO6

The crystal structures of two PbSb₂O₆-type compounds containing titanium, CdTi₂O₄(OH)₂ and LaTiSbO₆ were refined by X-ray powder diffraction data. For both compounds structure refinements with the space group were successful and the R-factors were R_WP = 6.46% and R_P = 4.90% for CdTi₂O₄(OH)₂ and R_WP = 9.55% and R_P = 7.17% for LaTiSbO₆. These crystal structures were the same as that of the typical PbSb₂O₆-type compound in spite of the existence of protons in the interlayer or two different metal ions in the layer.     

New palladium phosphate complexes: K2PdP2O7 and K3.5Pd2.25(P2O7)2 synthesis, single crystal structure and conductivity

Two new diphosphate complexes containing potassium and palladium, K₂PdP₂O₇ and K_3.5Pd_2.25(P₂O₇)₂, have been synthesized and characterized by single crystal X-ray diffraction. K₂PdP₂O₇ exists with layers formed of linked PdP₂O₇ polyhedra, between which are found the potassium ions. K_3.5Pd_2.25(P₂O₇)₂ with a Pd/P₂O₇ ratio of 1.125:1 crystallizes with tunnels of various sizes in which are found the potassium ions. Conductivity measurements reveal the material to be conducting.     

Multiferroic properties of ErMnO3

Measurements of magnetic and dielectric properties of single crystalline ErMnO₃ establish the Néel and ferroelectric transition temperatures to be 77 K and 588 K respectively. The dielectric constant of ErMnO₃ shows an anomalous jump at T_N. At higher temperatures, the dielectric constant undergoes a significant decrease on application of magnetic fields. The study clearly exhibits multiferroic and magnetoelectric nature of ErMnO₃.     

Synthesis, crystal structure and magnetic properties of a new lithium cobalt metaphosphate, LiCo(PO3)3

A new lithium cobalt metaphosphate, LiCo(PO₃)₃, is reported for the first time, which was discovered during the exploratory synthesis in Li-Co-P-O system by solid state reaction. The structure has been refined by powder X-ray Rietveld refinement method (P2₁2₁2₁, a = 8.5398(2) Å, b = 8.6326(2) Å and c = 8.3520(2) Å, Z = 4, R_p = 13.6%, R_wp = 19.4%, R_exp = 17.7%, S = 1.11, χ² = 1.23). It is isostructural with LiM(PO₃)₃ (M = Fe, Cu). It contains (PO₃)¹⁻ chains with the Co atoms localized in the octahedral sites, bridging four neighboring chains. The magnetic susceptibility measurement showed a typical paramagnetic behavior of high spin of Co²⁺, following the Curie-Weiss law in the temperature range of 5-300 K. Unlike the olivine type lithium cobalt phosphate, LiCoPO₄, cyclic voltammetry of LiCo(PO₃)₃ assembled in the coin-type cell showed no electrochemical activity in the voltage region of 1-5 V versus Li/Li⁺.     

Crystal structure and Eu/Tb doped luminescent properties of a new borate Ba3BiB9O18

Undoped and doped either by Eu³⁺ or Tb³⁺ bismuth borate Ba₃BiB₉O₁₈ was structurally characterized and analyzed by fluorescence spectroscopy. Belonging to synthetic borate member of the family Ba₃XB₉O₁₈, layers of planar triangular B₃O₆ groups connecting with deformed BaO₆ hexagons are interleaved by 9-coordinate Ba atoms, and 6-coordinate Bi atoms. Its crystal structure was determined and refined from powder X-ray diffraction data by the Rietveld method and the results showed that Ba₃BiB₉O₁₈ belongs to space group P6₃/m with unit cell dimensions of a = 7.1999(2) Å, c = 17.3567(6) Å, and z = 2. Curves of differential thermal analysis and thermogravimetric analysis showed that Ba₃BiB₉O₁₈ is a congruent melting compound and chemically stable above 728 °C. Ba₃Bi_1−xEu_xB₉O₁₈ and Ba₃Bi_1−xTb_xB₉O₁₈ form a continuous solid solution from x = 0.01 to x = 0.9. The ultraviolet excited photoluminescence intensity increased with both Eu³⁺ and Tb³⁺ concentration in the matrix of Ba₃BiB₉O₁₈. There may be an interesting correlation between spectroscopic properties and lattice structural features of doped Ba₃BiB₉O₁₈.     

Crystal structure and dynamical properties of a new tellurite: AgTlTeO3

The structure of a newly synthesized AgTlTeO₃ crystalline compound has been solved from single crystal X-ray diffraction data and refined to a final reliability factor R1 = 0.037. It was found having an orthorhombic Iba2 space group symmetry with unit cell parameters a = 14.708(7) Å, b = 10.745(6) Å, c = 5.166(3) Å, Z = 8. Its lattice is divided into separated AgTlTeO₃ sheets parallel to [0 1 0] which are formed by TeO₃ pyramids, TlO₄ disphenoids and AgO₆ octahedra sharing either corners or edges. At the same time, from the crystal chemistry point of view, it can be classified as a typical island-type compound made up from molecular-like [TeO₃]²⁻ ortho-anions weakly connected with Ag⁺ and Tl⁺ cations. The vibrational spectra and their interpretations complemented by the calculated elastic properties confirm this classification. The model-estimated piezoelectric constants allow characterizing AgTlTeO₃ as a strong pyroelectric structure.     

The crystal and magnetic structure of Ti-substituted LaCrO3

The crystal and magnetic structures of LaCrO₃ and La(Cr_0.90Ti_0.10)O₃ have been investigated between 5 and 350 K by means of neutron powder diffraction and DC magnetic measurements. Both compounds are characterized by an antiferromagnetic G_x-type ordering at low temperature. Structural features suggest the occurrence of Ti in the tetra-valent state. Despite the mixed valence induced by Ti-substitution leading to the occurrence of the Jahn-Teller species Cr²⁺, no evidence for long range ferromagnetism can be detected. On account of a miscibility gap, a higher degree of Ti-substitution at the Cr site cannot be achieved; as a consequence the solid state solubility of Ti in LaCrO₃ at 1573 K has been ascertained.     

Hydrothermal synthesis, characterization and magnetic properties of NaVGe2O6 and LiVGe2O6

Supercritical fluids are shown to be an excellent reaction media for the synthesis of novel solid state phases at intermediate temperatures. LiVGe₂O₆ and NaVGe₂O₆ have the common pyroxene structure composed of VO₆ linear chains. NaVGe₂O₆ crystallizes in the monoclinic space group C2/c with four formula units having cell dimensions a = 9.960(4) Å, b = 8.853(10) Å, c = 5.4861(10) Å, β = 106.403(3)°. The structure was refined until R = 0.0290 and R_w = 0.0370. For LiVGe₂O₆ in space group P2₁/c: a = 9.8508(7) Å, b = 8.754(3) Å, c = 5.3948(13) Å, β = 108(3)°, R = 0.0240 and R_w = 0.0250. The compounds contain edge-shared VO₆ octahedral chains and corner-shared GeO₄ tetrahedral chains. The presence of these VO₆ chains results in spin-Peierls distortion. Structural and physical characterization of the compounds are reported.     

Preparation and crystal structure of a new bismuth vanadate, Bi3.33(VO4)2O2

Single crystals of a new bismuth vanadate, Bi_3.33(VO₄)₂O₂ was prepared by hydrothermal reaction using a hydrated sodium bismuthate, NaBiO₃·nH₂O as one of the starting compounds. The crystal structure was determined by using single crystal X-ray diffraction data. This compound crystallizes in the triclinic space group (#2) with a = 7.114(1), b = 7.844(2), c = 9.372(2) Å, α = 106.090(7), β = 94.468(7) and γ = 112.506(8)°, Z = 2 and the final R factors are R1 = 0.052 and wR2 = 0.14 for 2085 unique reflections. The crystal structure is composed by four bismuth atoms with the coordination number of 6 or 8 and two VO₄ tetrahedra, and one of four bismuth atoms is statistically distributed in the splitting sites with the distance of 0.83 Å. This compound exhibited photocatalytic behavior for decomposition of phenol under visible light irradiation and its activity was less than that of monoclinic BiVO₄.     

Microwave-hydrothermal synthesis of γ-Fe2O3 nanoparticles and their magnetic properties

Nanosized γ-Fe₂O₃ is synthesized by the microwave-hydrothermal method. Powder X-ray diffraction and transmission electron microscopic studies showed that the average particle size is 10 nm. Magnetic studies reveal that the γ-Fe₂O₃ nanoparticles are superparamagnetic at room temperature, with a superparamagnetic blocking temperature of 200 K. The magnetic characteristics of the nanoparticles indicate their strongly interacting nature.     

Synthesis, structure and magnetic properties of a new iron phosphonate-oxalate with 3D framework: [Fe(O3PCH3)(C2O4)0.5(H2O)]

A new iron phosphonate-oxalate [Fe(O₃PCH₃)(C₂O₄)_0.5(H₂O)] (1), has been synthesized under hydrothermal condition. The single-crystal X-ray diffraction studies reveal that 1 consists of layers of vertex-linked FeO₆ octahedra and O₃PC tetrahedra, which are further connected by bis-chelate oxalate bridges, giving to a 3D structure with 10-membered channels. Crystal data: monoclinic, P2₁/n (no. 14), a = 4.851(2) Å, b = 16.803(7) Å, c = 7.941(4) Å, β = 107.516(6)°, V = 617.2(5) Å³, Z = 4, R₁ = 0.0337 and wR₂=0.0874 for 1251 reflections [I > 2σ(I)]. Mössbauer spectroscopy measurement confirms the existence of high-spin Fe(III) in 1. Magnetic studies show that 1 exhibits weak ferromagnetism with T_N = 30 K due to a weak spin canting.     

Crystal and magnetic study of the disordered perovskites Ca(Mn0.5Sb0.5)O3 and Ca(Fe0.5Sb0.5)O3

We have investigated the double perovskites Ca₂MSbO₆ (M = Mn, Fe) that have been prepared by solid-state reaction (M = Fe) and wet chemistry procedures (M = Mn). The crystal and magnetic structures have been studied from X-ray (XRD) and neutron powder diffraction (NPD) data. Rietveld refinements show that the crystal structures are orthorhombic (space group Pbnm) with complete disorder of M and Sb cations, so the formula should be rewritten as Ca(M_0.5Sb_0.5)O₃. Due to this disorder no evidences of Jahn-Teller distortion can be observed in the MnO₆ octahedra of Ca(Mn_0.5Sb_0.5)O₃, in contrast with the ordered double perovskite Sr₂MnSbO₆. Ca(Fe_0.5Sb_0.5)O₃ behaves as an antiferromagnet with an ordered magnetic moment for Fe³⁺ of 1.53(4)μ_B and a propagation vector k = 0, as investigated by low-temperature NPD. The antiferromagnetic ordering is a result of the high degree of Fe/Sb anti-site disorder of the sample, which originates the spontaneous formation of Fe-rich islands, characterized by the presence of strong Fe-O-Fe antiferromagnetic couplings with enough long-range coherence to produce a magnetic contribution perceptible by NPD. By contrast, the magnetic structure of Ca(Mn_0.5Sb_0.5)O₃ cannot be observed by low-temperature NPD because the magnitude of the ordered magnetic moments is below the detection threshold for neutrons.     

Synthesis and characterization of Bi2Fe4O9 powders

Bi₂Fe₄O₉ have been successfully prepared using ethylenediaminetetraacetic (EDTA) acid as a chelating agent and ethylene glycol as an esterification agent. Heating of a mixed solution of EDTA, ethylene glycol, and nitrates of iron and bismuth at 140 °C produced a transparent polymeric resin without any precipitation, which after pyrolysis at 250 °C was converted to a powder precursor for Bi₂Fe₄O₉. The precursors were heated at 400–800 °C in air to obtain Bi₂Fe₄O₉ powder and differential scanning calorimetry (DSC), thermogravimetric (TG), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) techniques were used to characterize the precursors and the derived oxide powders. XRD analysis showed that well-crystallized and single-phase Bi₂Fe₄O₉ with orthorhombic symmetry was obtained at 700 °C for 2 h and BiFeO₃ and Fe₂O₃/FeCO₃ were intermediate phases before the formation of Bi₂Fe₄O₉. Bi₂Fe₄O₉ powders show weak ferromagnetism at room temperature.     

Preparation, structure and luminescent properties of a new potassium yttrium borate K3Y3(BO3)4

A new yttrium borate compound K₃Y₃(BO₃)₄ has been obtained in the K₂O-Y₂O₃-B₂O₃ ternary system. Its structure, determined from single crystal X-ray diffraction data, shows that it belongs to space group P2₁/c with unit cell dimensions of a = 10.4667(16) Å, b = 17.361(3) Å, c = 13.781(2) Å and β = 110.548(8)°. The structure consists sheets of [Y₈B₈O₂₄]_∞ linked by out of sheet BO₃ groups and Y ions to form a three-dimensional framework. The luminescent properties of Eu³⁺ and Tb³⁺ doped K₃Y₃(BO₃)₄ materials have also been studied.