Single-crystal oxoborate (Pb3O)2(BO3)2WO4: Growth and characterization

An oxoborate, (Pb₃O)₂(BO₃)₂WO₄, has been prepared by solid-state reaction methods below 620 °C. Single-crystal XRD analysis shows that it crystallizes in the orthorhombic group Cmcm with a = 18.480(4) Å, b = 6.3567(13) Å, c = 11.672(2) Å, Z = 4. The crystal structure is composed of one-dimensional 1/∞ [Pb₃O]⁴⁺ chains formed by corner-sharing OPb₄ tetrahedra. BO₃ and WO₄ groups are located around the chains to hold them together via PbO bonds. The IR spectra further confirmed the presence of BO₃ groups. Furthermore we have performed theoretical calculations by employing the all-electron full potential linearized augmented plane wave (FP-LAPW) method to solve the Kohn Sham equations. Starting from our XRD data we have optimized the atomic positions by minimizing the forces. These are used to calculate the electronic band structure, the atomic site-decomposed density of states, electron charge density and the chemical bonding features. The calculated electronic band structure and densities of states suggest that this oxoborate possesses a wide energy band gap. The valence band maxima and the conduction band minima are located at Y point in the Brillouin zone resulting in a direct energy band gap of 2.3 eV using the local density approximation and 2.6 eV for the Engel–Vosko generalized gradient approximation. This compares well with our experimentally measured energy band gap of 2.9 eV. From our calculated electron charge density distribution, we obtain an image of the electron clouds that surround the molecules in the unit cell of the crystal. The chemical bonding features were analyzed and the substantial covalent interactions are observed between Pb and O, B and O and W and O atoms.     

Effects of WO3 addition on the structure and electrical properties of Pb3O4 modified PZT–PFW–PMN piezoelectric ceramics

The ceramics were prepared successfully by Pb₃O₄ and WO₃ additions to 0.90Pb(Zr,Ti)O₃–0.03Pb(Fe_2/3W_1/3)O₃–0.07Pb(Mn_1/3Nb_2/3)O₃ (0.90PZT–0.03PFW–0.07PMN). Effects of the additions on the structure, bulk density and electrical properties of ceramics were investigated. The results revealed that the proper additions of WO₃ with 2.0 wt.% Pb₃O₄ excess could form liquid phase that promoted the densification of the ceramics. The fracture mode changed from transgranular to intergranular as increasing WO₃ with 2.0 wt.% Pb₃O₄ excess. The piezoelectric and dielectric properties were also promoted by excess of Pb₃O₄ and WO₃ additions. The optimized electrical properties were obtained at excess of 2.0 wt.% Pb₃O₄ and 0.15 wt.% WO₃. The parameters were as follows: d₃₃ = 351 pC/N, K_p = 0.64, Q_m = 1882, ɛ_r = 1798, tan δ = 0.0052, P_r = 19.94 μC/cm² and E_c = 11.98 kV/cm, which shows high K_p, Q_m, d₃₃ and low tan δ can be obtained simultaneously by adding WO₃ addition to Pb₃O₄ modified PZT–PFW–PMN system.     

Synthesis and structure determination of new open-framework chromium carboxylate MIL-105 or CrIII(OH)·{O2C–C6(CH3)4–CO2}·nH2O

Two new three-dimensional chromium(III) dicarboxylate, MIL-105 or Cr^III(OH)·{O₂C-C₆(CH₃)₄-CO₂}·nH₂O, have been obtained under hydrothermal conditions, and their structures solved using X-ray powder diffraction data. Both solids are structural analogs of the known Cr benzenedicarboxylate compound (MIL-53). Both contain trans corner-sharing CrO₄(OH)₂ octahedral chains connected by tetramethylterephthalate di-anions. Each chain is linked by the ligands to four other chains to form a three-dimensional framework with an array of 1D pores channels. The pores of the high temperature form of the solid, MIL-105ht, are empty. However, MIL-105ht re-hydrates at room temperature to finally give MIL-105lt with pores channels filled with free water molecules (lt: low temperature form; ht: high temperature form). The thermal behaviour of the two solids has been investigated using TGA. Crystal data for MIL-105ht: monoclinic space group C2/c with a = 19.653(1) Å, b = 9.984(1) Å, c = 6.970(1) Å, β = 110.67(1)° and Z = 4. Crystal data for MIL-105lt: orthorhombic space group Pnam with a = 17.892(1) Å, b = 11.165(1) Å, c = 6.916(1) Å and Z = 4.     

Variants of the Bi6TiP2O16 structure: The preparation and crystal structure of the isomorph Bi6(Mn0.6Bi0.4)P2O15

Compounds with the composition Bi₆(Bi_1−yM_y)X₂O_16−z, M = transition metal or Pb, X = P, V, As, display pseudo-tetragonal crystal systems. They are, however, monoclinic with space group I2 and the heavy atom positions mimic the δ-Bi₂O₃ structure. The title compound is monoclinic, a = 11.284(2) Å, b = 5.4259(11) Å, c = 11.112(2) Å, β = 96.25(3)°, I2, Z = 2. Least-squares refinement of single-crystal X-ray diffraction data on F² converged to R1 = 0.050, wR2 = 0.130. The crystal is twinned by two-fold rotation about [0 1 0] and each twin consists of its inverted component forming a racemate. The structure consists of chains of edge sharing (OBi₄) tetrahedra parallel to [1 0 −1]. The chains are bridged parallel to [1 0 1] by linked PO₄ tetrahedra and (Mn/Bi)O₆ octahedra parallel to [1 0 −1], into a three-dimensional structure. The lone-pair electrons of adjacent Bi atoms along the chain point in opposite directions along the b-axis. The Bi atoms are in distorted trigonal prismatic coordination that has one or two faces capped. The BiO bond lengths vary from 2.08(5) to 3.05(2) Å. The Mn/Bi atoms are disordered around the two-fold axis. Three oxygen atom sites contain vacancies.     

Ba2La2TiNb2O12: A new microwave dielectric of A4B3O12-type cation-deficient perovskites

A new A₄B₃O₁₂-type cation-deficient perovskite Ba₂La₂TiNb₂O₁₂ was prepared by the conventional solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM). The compound crystallizes in the trigonal system with unit cell parameter a = 5.6726(3) Å, c = 27.740(2) Å, V = 773.04(9) ų and Z = 3. The microwave dielectric properties of the ceramic were studied using a network analyzer, and it shows a high dielectric constant of 42.70, a high quality factor with Q × f of 31,130 GHz, and a small negative τ_f of − 4.2 ppm °C^− 1.     

Preparation,phase structure and microwave dielectric properties of CoLi2/3Ti4/3O4 ceramic

A new low loss microwave dielectric ceramic with composition of CoLi_2/3Ti_4/3O₄ was prepared by a conventional solid-state reaction method. The compound has a cubic spinel structure [Fd-3m (227)] similar to MgFe₂O₄ with lattice parameters of a = 8.3939 Å, V = 591.42 Å³, Z = 8 and ρ = 4.30 g/cm³. This ceramic has a low sintering temperature (～1050 °C) and good microwave dielectric properties with relative permittivity of 21.4, Q × f value of 35,000 GHz and τ_f value of ?22 ppm/°C. Furthermore, the addition of BaCu(B₂O₅) (BCB) can effectively lower the sintering temperature from 1050 °C to 900 °C and does not induce much degradation of the microwave dielectric properties. Compatibility with Ag electrode indicates that the BCB added CoLi_2/3Ti_4/3O₄ ceramics are good candidates for LTCC applications.     

Hydrothermal synthesis,crystal structure and characterization of LiCoP5O14·H2O: A new condensed layered penta phosphate crystals

A new family of condensed hydrated lithium cobalt penta phosphate (LiCoP₅O₁₄·H₂O) crystals were synthesized by hydrothermal technique and characterized by X-ray diffraction method. The compound crystallizes in monoclinic system with space group P21/c and cell parameters a = 10.788(4) Å, b = 9.761(3) Å, c = 9.788(5) Å, β = 101.249(1) Å, Z = 4, exhibiting layer type polymeric structure. DTA study indicates that this compound has low thermal stability and magnetically frequency dependent paramagnetic behaviour.     

Fluorine intercalation in the n = 1 and n = 2 layered manganites Sr2MnO3.5+x and Sr3Mn2O6

Fluorine insertion into the oxygen defect superstructure manganite Sr₂MnO_3.5+x has been shown by transmission electron microscopy (TEM) to result in two levels of fluorination. In the higher fluorine content sections, the fluorine anions displace oxygen anions from their apical positions into the equatorial vacancies, thus destroying the superstructure and reverting to a K₂NiF₄-type structure (a = 3.8210(1) Å and c = 12.686(1) Å). Conversely, lower fluorine content sections retain the Sr₂MnO_3.5+x defect superstructure, crystallising in the P2₁/c space group. Fluorine intercalation into the reduced double-layer manganite Sr₃Mn₂O₆ occurs in a step-wise fashion according to the general formula Sr₃Mn₂O₆F_y with y = 1, 2, and 3. It is proposed that the y = 1 phase (a = 3.815(1) Å, c = 20.29(2) Å) is produced by the filling of all the equatorial oxygen vacancies by fluorine atoms whilst the y = 2 phase (a = 3.8222(2) Å, c = 21.2435(3) Å) has a random distribution of fluorine anions throughout both interstitial rocksalt and equatorial sites. Neutron powder diffraction data suggest that the fully fluorinated y = 3 phase (a = 3.8157(6) Å, c = 23.666(4) Å) corresponds to the complete occupation of all the equatorial oxygen vacancies and the interstitial sites by intercalated fluorine.     

Synthesis,crystal structure refinement,electrical and magnetic properties of BaV13O18 and SrV13O18

Polycrystalline samples of BaV₁₃O₁₈ and SrV₁₃O₁₈ were prepared by solid-state reaction of BaCO₃, SrCO₃, V₂O₅ and V at 1773–2073 K in flowing Ar. The crystal structures of BaV₁₃O₁₈ (R-3, a_h=12.6293(10) Å, c_h=7.0121(4) Å) and SrV₁₃O₁₈ (a_h=12.5491(7) Å, c_h=6.9878(3) Å) were refined by the Rietveld method using X-ray diffraction data. BaV₁₃O₁₈ exhibited semiconducting behavior with electrical resistivity from 5.8×10⁻³ to 2.7×10⁻³ Ω cm at 100–300 K. Electrical resistivity of SrV₁₃O₁₈ ranged from 1.5×10⁻³ to 1.8×10⁻³ Ω cm, and it increased slightly up to around 250 K and decreased above 250 K with increasing temperature. Negative Seebeck coefficients of both compounds at 100–300 K indicated that electron was the dominant carrier. BaV₁₃O₁₈ and SrV₁₃O₁₈ showed paramagnetism with the effective magnetic moment of 0.11μ_B and 0.15μ_B, respectively, at 10–100 K.     

High-pressure synthesis and magnetic properties of complex oxide Y2Cd2/3Re4/3O7

A new complex oxide Y₂Cd_2/3Re_4/3O₇ with hexagonal cell parameters a = 7.3564(2) Å, c = 17.7092(5) Å (space group P3₁21, z = 6, zirkelite structure type) was synthesized from Y₃ReO₈, ReO₂, metallic Re and CdO under pressure 6 GPa and temperature 1500 °C. Magnetic susceptibility measured in the temperature range from 2 to 300 K depends little on temperature above ∼50 K and is indicative of a delocalized or intermediate character of d electrons of Re⁵⁺ cations.     

Synthesis and characterization of a one-dimensional inorganic–organic hybrid iron phosphate: [Fe(bipy)(HPO4)(H2PO4)] (bipy = 2,2′-bipyridyl) with anti-ferromagnetic property

A coordinated iron phosphate, Fe(bipy)(HPO₄)(H₂PO₄) (I), has been hydrothermally synthesized and characterized by elemental analysis, thermogravimetric analysis, and single crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P2₁/n (No. 14), with cell parameters M = 405.00, a = 10.904(4) Å, b = 6.4210(2) Å, c = 19.294(9) Å, β = 101.24(4) ų, V = 1324.9(9) ų, Z = 4, R₁ [I > 2((I)) = 0.0357, wR₂ [I > 2((I)) = 0.0717. This compound displays a new structure of ladder-like chains, in which each one-dimensional chain is constituted by the distorted octahedral units of Fe³⁺ bridged through PO₄ tetrahedra. The bipy ligands in the compound bind in a bidentate fashion to the iron atoms and the ladder-like structure of the compound extends into a three-dimensional supramolecular array via π–π stacking interactions of bipy ligands and strong hydrogen bonding between the chains. Mössbauer spectroscopy shows the presence of Fe³⁺ in the octahedral coordination. Magnetic susceptibility measurements show that this material may model as anti-ferromagnetic.     

Ca25Co22O56(OH)28: A layered misfit compound

The high pressure synthesis, structure and magnetic properties of Ca₂₅Co₂₂O₅₆(OH)₂₈ are reported. The compound has a misfit structure, consisting of double, square calcium oxide hydroxide rock-salt-like layers between hexagonal CoO₂ layers. The misfit compound crystallizes in the monoclinic space group C2/m, and can be characterized by the coexistence of two subsystems with common a = 4.893(5) Å, c = 8.825(9) Å and β = 95.745(8) parameters, and different b parameters: b_RS = 4.894(5) Å, and b_HEX = 2.809(3) Å, for the rock-salt and hexagonal type planes, respectively. The compound shows Curie–Weiss paramagnetism with an antiferromagnetic Weiss temperature of −43 K and a reduced Co moment. Substantial deviations from Curie–Weiss behavior are seen below 50 K with no indication of magnetic ordering. No superconductivity was observed down to a temperature of 2 K.     

Novel two-dimensional metal-organic framework with unprecedented trimeric building unit constructed from bridging water molecules

A novel two-dimensional nickel trimesate (1,3,5-benzenetricarboxylate), Ni₃(C₉O₆H₃)₂(H₂O)₈, has been obtained by solvothermal route. Its structure is built up from linear trimers of nickel, {Ni₃O₈(μ₂–OH₂)₂(H₂O)₆}, connected by trimesate anions. It crystallizes in the triclinic system, space group P-1, with a = 6.6960(3), b = 9.6446(3), c = 10.1114(3) Å, α = 112.638(1)°, β = 94.008(1)°, γ = 106.476(1)°, V = 565.99(4) Å³. Synthesis, X-ray structure determination, thermogravimetric analysis and magnetic properties are presented.     

Synthesis,characterization and crystal structure of a novel Strandberg-type polyoxoselenomolybdate Rb4[Se2Mo5O21]·2H2O

An inorganic compound formulated as Rb₄[Se₂Mo₅O₂₁]·2H₂O (1) has been isolated by conventional solution method and structurally characterized by single-crystal X-ray diffraction methods, scanning electron microscopy (SEM), powder XRD, IR, UV–vis spectra, and cyclic voltammetry measurements. This compound crystallizes in the monoclinic system, space group C2 with unit a = 19.701 (3) Å, b = 10.296 (2) Å, c = 12.134 (4) Å, β = 106.96 (2)° and Z = 4. The crystal structure of (1) is built up from a Strandberg clusters connected through hydrogen-bonding interactions into a three-dimensional supramolecular network.     

Preparation,crystal structure and characterization of α-NaSbP2S6 and β-NaSbP2S6 phases

The new phases α-NaSbP₂S₆ and β-NaSbP₂S₆ were synthesized by ceramic and reactive flux methods at 773 K. The structures of α-NaSbP₂S₆ and β-NaSbP₂S₆ were determined by the single-crystal X-ray diffraction technique. α-NaSbP₂S₆ crystallizes in the monoclinic space group P2₁/c with a = 11.231(2) Å, b = 7.2807(15) Å, c = 11.640(2) Å, β = 108.99(3)°, V = 900.0(3) Å³ and z = 4. β-NaSbP₂S₆ crystallizes in the monoclinic space group P2₁ with a = 6.6167(13) Å, b = 7.3993(15) Å, c = 9.895(2) Å, β = 92.12(3) °, V = 484.10(17) Å³ and z = 2.The α- and β-phases of NaSbP₂S₆ are closely related, the main difference lies in the stacking of the [Sb[P₂S₆]]_nⁿ⁻ layers. The structure of α-NaSbP₂S₆ consists of two condensed layers (MPS₃ type) to give an ABAB… sequence with Na⁺ cations located in the interlayer space. The packing of β-NaSbP₂S₆ is formed by monolayers of [Sb[P₂S₆]]_nⁿ⁻ stacked in an AA… fashion separated by a layer of Na⁺ cations. Both phases are derivates of the M¹⁺M³⁺P₂Q₆ family.The optical band gaps of α-NaSbP₂S₆ and β-NaSbP₂S₆ were determined by UV–vis diffuse reflectance measurements to be 2.17 and 2.25 eV, respectively.     

Synthesis and characterization of a new p-phenylenediammonium dihydrogenmonophosphate [p-NH3C6H4NH3][H2PO4]2

Chemical preparation, crystal structure and NMR spectroscopy of a new organic cation p-phenylenediammonium monophosphate [p-NH₃C₆H₄NH₃][H₂PO₄]₂ are presented. This new compound crystallizes in the orthorhombic system, with the space group Pnma and the following parameters: a = 7.970 (2) Å; b = 22.770 (7) Å; c = 7.000 (7) Å, V = 1270.3 (11) Å³, Z = 4 and D_x = 1.590 g cm⁻³. The crystal structure has been determined and refined to R = 0.043 and R_(w) = 0.057 using 2623 independent reflections. The structural arrangement can be described as inorganic layers of (H₈P₄O₁₆)⁴⁻ units, parallel to (a, c) planes. The organic groups (p-H₃NC₆H₄NH₃)²⁺are anchored between the phosphoric layers to form a three-dimensional infinite network. This compound is also investigated by IR and solid-state ¹H, ¹³C and ³¹P MAS NMR spectroscopies. The ab initio method is used in the calculation of chemical shifts.     

Preparation,characterization and dielectric properties of Ba5LnZnTa9O30 (Ln=La,Sm) ceramics

Ba₅LnZnTa₉O₃₀ (Ln=La, Sm) ceramics were prepared by high temperature solid-state reaction route. The samples were characterized by X-ray diffraction, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) methods. They belong to paraelectric phase of filled tetragonal TB structure at room temperature with unit cell a=12.5909(4) Å, c=3.9622(2) Å for Ba₅LaZnTa₉O₃₀; and a=12.5777(4) Å, c=3.9544(2) Å for Ba₅SmZnTa₉O₃₀. At 1 MHz, Ba₅LaZnTa₉O₃₀ has high dielectric constants of 89 with low dielectric loss 0.0067, and temperature coefficients of the dielectric constant (τ_ε) −811 ppm °C⁻¹; Ba₅LaZnTa₉O₃₀ has dielectric constants of 74 with low dielectric loss 0.0035, and τ_ε −474 ppm °C⁻¹.     

Structural,thermal, spectroscopic and magnetic studies of the (C2N2H10)0.5[FexV1−x(HPO3)2] (x = 0.26, 0.52, 0.74) solid solution

The (C₂N₂H₁₀)_0.5[Fe_xV_1−x(HPO₃)₂] (x = 0.26, 0.52 0.74) compounds have been obtained by mild solvothermal conditions in the form of micro-crystalline powder with brown color. The crystal structures were refined by X-ray powder diffraction data using the Rietveld method. The compounds crystallize in the monoclinic system, space group P2/c with the unit-cell parameters, a = 9.262(5) Å, b = 8.823(5) Å, c = 9.714(6) Å, β = 120.84(3)°; a = 9.245(1) Å, b = 8.823(1) Å, c = 9.698(1)Å, β = 120.80(1)° and, a = 9.254(4)Å, b = 8.822(4)Å, c = 9.702(4)Å, β = 120.73(3)° for (C₂N₂H₁₀)_0.5[Fe_0.26V_0.74 (HPO₃)₂] (1), (C₂N₂H₁₀)_0.5[Fe_0.52V_0.48(HPO₃)₂] (2), and (C₂N₂H₁₀)_0.5[Fe_0.74V_0.26(HPO₃)₂] (3). The compounds show an open crystalline structure with three-dimensional character, whose formula for the anionic inorganic skeleton is [M(HPO₃)₂]²⁻. The inorganic framework is formed by [MO₆] octahedra inter-connected by phosphite groups. The structure of the compounds exhibits channels extended along the [1 0 0] and [0 0 1] directions and the ethylendiammonium cations are located inside these channels, linked through hydrogen bonds and ionic interactions. The infrared spectra show the bands corresponding to the stretching (P–H) vibration of the phosphite group and the band corresponding to the deformation mode of the ethylendiammonium cation, δ(NH₃⁺). The thermal and thermodiffractometric behavior show that the compounds are stable up to approximately 300 °C, at higher temperatures the decomposition of the crystal structure by calcination of the organic cation starts. The diffuse reflectance spectra show bands of the V³⁺ ion (d²), and a band of the Fe³⁺ ion (d⁵), in a slightly distorted octahedral symmetry. The values of the Dq and Racah parameters (B and C) have been calculated for the V(III) cation. Magnetic measurements were performed on a powdered sample from 5 to 300 K at magnetic fields 1000, 500 and 100 G, in the ZFC and FC modes. At the magnetic field of 1000 G antiferromagnetic interactions were observed, but at 100 G have been detected higher values of the χ_m in the FC mode than those observed in the ZFC one, indicating the existence of a dominant ferromagnetic component at low temperature. The magnetization measurements show hystheresis loops at 5 K, with values of the remanent magnetization and coercive field of 1.91 emu/mol and 23 Gauss for (1), 25 emu/mol and 300 Gauss for (2), and 3 emu/mol and 50 Gauss for the compound (3).     

Optical constants and crystal chemical parameters of Sc2W3O12

The refractive indices of Sc₂W₃O₁₂, measured at wavelengths of 435.8–643.8 nm, were used to calculate n_a = 1.7331, n_b = 1.7510, n_c = 1.7586 at λ = 589.3 nm and n_∞ values at λ = ∞ from a one-term Sellmeier equation. Mean refractive indices, 〈n_D〉, and mean dispersion values, 〈A〉, are, respectively, 1.7475 and 110 × 10^?16 m². Total electronic polarizabilities, α_obs, were calculated from n_∞ and the Lorenz–Lorentz equation. The unusually large difference between the observed polarizability of 28.415 Å³ and the calculated total polarizability α_T of 26.74 Å³ (Δ = +6.3%) is attributed to (1) a large M–O–W angle, and (2) a high degree of W 5d–O 2p and Sc nd–O 2p hybridization, where n signifies unspecified Sc d orbitals.