Chemical preparation, crystal structure and characterization of the new sodium ytterbium cyclotriphosphate Na3Yb(P3O9)2·9H2O

Chemical preparation and crystal structure are reported for a new lanthanide cyclotriphosphate Na₃Yb(P₃O₉)₂·9H₂O. This salt crystallizes in the trigonal system, space group with the following parameters: a = 30.933(2), c = 12.8282(5) Å. The crystal structure was refined to R₁ = 0.0432 using 1782 reflections with I > 2 σ(I). In the Na₃Yb(P₃O₉)₂·9H₂O structure, the phosphoric ring anions, located around the axis are interconnected by YbO₈ dodecahedra and NaO₆ and NaO₇ polyhedra to build, around the threefold axis, large channels parallel to the c axis. All the nine water molecules in the present arrangement participate in the coordination spheres of the associated cations. The thermogravimetric analysis shows that the removal of these water molecules occurs in three stages between 305 and 736 K.The vibrational study by IR absorption spectroscopy of Na₃Yb(P₃O₉)₂·9H₂O is also reported.     

Synthesis and characterization of a new organic dihydrogenomonophosphate [3,5-(CH3O)2C6H3NH3]2(H2PO4)2

Chemical preparation, crystal structure, calorimetric studies and spectroscopic investigation are given for a new organic cation dihydrogenomonophosphate [3,5-(CH₃O)₂C₆H₃NH₃]₂(H₂PO₄)₂. This compound is triclinic with the following unit cell parameters: a=9.030(6) Å, b=16.124(5) Å, c=8.868(3) Å, α=75.04(3)°, β=110.71(4)°, γ=104.61(1)°, Z=4, V=1148.0(1) Å³, Z=2 and ρ_cal.=1.454 g cm⁻³. Crystal structure was solved and refined to R=0.04, 2752 independent reflections. The atomic arrangement can be described as inorganic layers of H₂PO₄⁻ anions parallel to planes, between which are located the organic groups. Solid-state and MAS-NMR spectroscopies are in agreement with the X-ray structure. Ab initio calculations allow the attribution of the phosphorous and carbon signals to the independent crystallographic sites and to the various atoms of the organic groups.     

New compounds Cu2MnTi3S8 and Cu2NiTi3S8 with thiospinel structure

Cu₂MnTi₃S₈ and Cu₂NiTi₃S₈ compounds were prepared by high-temperature synthesis. The crystal structure of these quaternary phases was investigated by X-ray powder diffraction. The compounds are described in the thiospinel structure (space group ) with the lattice constants a = 1.00353(1) nm (Cu₂MnTi₃S₈) and a = 0.99716(1) nm (Cu₂NiTi₃S₈). The atomic parameters were calculated in anisotropic approximation (R_I = 0.0456 and R_I = 0.0520 for Cu₂MnTi₃S₈ and Cu₂NiTi₃S₈, respectively).     

The system Ag2Se-Ho2Se3 in the 0-50 mol.% Ho2Se3 range and the crystal structure of two polymorphic forms of AgHoSe2

The phase diagram of the Ag₂Se-Ho₂Se₃ system in the range of 0-50 mol.% Ho₂Se₃ was constructed with the results of XRD and differential thermal analysis. A dimorphous compound exists in the system at the equimolar ratio of the components. The investigated part of the Ag₂Se-AgHoSe₂ diagram is of the eutectic type with the eutectic coordinates 7 mol.% Ho₂Se₃ and 1125 K. The crystal structure of the high-temperature modification of AgHoSe₂ was studied by X-ray powder diffraction method. α-AgHoSe₂ is described as a NaCl structure (space group ) with the lattice parameter а = 5.7623(3) Å. Atomic parameters were calculated in the isotropic approximation (R_I = 0.0434 and R_Р = 0.0636). The crystal structure of β-AgHoSe₂ was determined by X-ray structure analysis and was refined to R = 0.0487.     

Structural characterization and AC conductivity of bis tetrapropylammonium hexachlorado-dicadmate, [N(C3H7)4]2Cd2Cl6

Synthesis, crystal structure, vibrational study, ¹³C, ¹¹¹Cd CP-MAS-NMR analysis and electrical properties of the compound [N(C₃H₇)₄]₂Cd₂Cl₆, are reported. The latter crystallizes in the triclinic system (space group , Z = 2) with the following unit cell dimensions: a = 9.530(1) Å, b = 11.744(1) Å, c = 17.433(1) Å, α = 79.31(1)°, β = 84.00(1)° and γ = 80.32(1)°. Besides, its structure was solved using 6445 independent reflections down to R = 0.037. The atomic arrangement can be described by alternating organic and inorganic layers parallel to the plan, made up of tetrapropylammonium groups and Cd₂Cl₆ dimers, respectively. In crystal structure, the inorganic layer, built up by Cd₂Cl₆ dimers, is connected to the organic ones through van der Waals interaction in order to build cation-anion-cation cohesion. Impedance spectroscopy study, reported in the sample, reveals that the conduction in the material is due to a hopping process. The temperature and frequency dependence of dielectric constants of the single crystal sample has been investigated to determine some related parameters to the dielectric relaxation.     

Thermochemical studies on SrFe12O19(s)

The citrate-nitrate gel combustion route was used to prepare SrFe₁₂O₁₉(s) powder sample and the compound was characterized by X-ray diffraction analysis. A solid-state electrochemical cell of the type: (−)Pt, O₂(g)/{CaO(s) + CaF₂(s)}//CaF₂(s)//{SrFe₁₂O₁₉(s) + SrF₂(s) + Fe₂O₃(s)}/O₂(g), Pt(+) was used for the measurement of emf as a function of temperature from 984 to 1151 K. The standard molar Gibbs energy of formation of SrFe₁₂O₁₉(s) was calculated as a function of temperature from the emf data and is given by: (SrFe₁₂O₁₉, s, T)/kJ mol⁻¹ (±1.3) = −5453.5 + 1.5267 × (T/K). Standard molar heat capacity of SrFe₁₂O₁₉(s) was determined in two different temperature ranges 130-325 K and 310-820 K using a heat flux type differential scanning calorimeter (DSC). A heat capacity anomaly was observed at 732 K, which has been attributed to the magnetic order-disorder transition from ferrimagnetic state to paramagnetic state. The standard molar enthalpy of formation, (298.15 K) and the standard molar entropy, (298.15 K) of SrFe₁₂O₁₉(s) were calculated by second law method and the values are −5545.2 kJ mol⁻¹ and 633.1 J K⁻¹ mol⁻¹, respectively.     

Spectroscopic and glass transition investigations on Nd-doped NaF-Na2O-B2O3 glasses

New developments in photonic technology need new materials for various applications. In the present report, Nd³⁺-doped NaF-Na₂O-B₂O₃ glasses were prepared and the spectroscopic and glass transition properties were analysed. The Fourier transform infrared spectral studies reveal that the glass contains BO₃ and BO₄ units as the local structures and the Na⁺ ions as the network modifiers. The absorption studies were carried out by using Judd-Ofelt theory, the experimental and theoretical oscillator strengths were also calculated. The emission spectral study was done for the 1 mol% Nd-doped glass and the spontaneous emission probability and stimulated emission cross-sections for the , transitions were calculated using the J-O parameters.     

The crystal structure of eulytite Pb3BiV3O12

The crystal structure of Pb₃BiV₃O₁₂ was solved using single-crystal X-ray diffraction technique. The compound crystallizes in the cubic system (No. 220) with eulytite structure with a = 10.7490(7) Å, V = 1241.95(14) Å³ and Z = 4. The final R₁ value of 0.0198 (wR₂=0.0384) was achieved for 359 independent reflections during the structure refinement. The Pb²⁺ and Bi³⁺ cations occupy the special position (16c) while the oxygen anions occupy the general position (48e) in the crystal structure. Unlike many other eulytite compounds, all the crystallographic positions are fully occupied. The structure consists of edge-shared Pb/Bi octahedra linked at the corners to independent [VO₄]³⁻ tetrahedra units, generating a eulytite-type network in the crystal lattice.     

Crystal structures and phase transitions in Ba2HoTaO6

The structure of the cation-ordered double perovskite Ba₂HoTaO₆ was examined using synchrotron X-ray powder diffraction at fine temperature intervals over the range of 90-300 K. Ba₂HoTaO₆ has a cubic structure in space group at room temperature. A proper ferroelastic phase transition to I4/m tetragonal symmetry occurs near approximately 260 K. Analysis of the spontaneous tetragonal strain versus temperature indicated that the phase transition is second order in nature.     

GexNbSe2 and GexNbS2 intercalation compounds

The structures of two intercalation compounds, Ge_∼0.2NbSe₂ and Ge_∼0.3NbS₂ were investigated by single crystal X-ray diffraction and electron microscopy (selected area electron diffraction (SAED), high resolution electron microscopy (HRTEM) and X-ray microanalysis by energy dispersive spectroscopy (XEDS)). Crystal structure determinations of the average structure of the intercalation compounds 2H-Ge_0.217NbSe₂ and 4H-Ge_0.288NbS₂ are reported: the selenide compound crystallizes in the space group P6₃/mmc with a = 3.4560(9) Å and c = 12.966(3) Å and adopts the 2H-NbSe₂ structure-type, while the sulfide compound crystallizes in the P6₃mc space group, with a = 3.3392(9) Å and c = 25.404(7) Å with a structure-type 4H_c-NbS₂ which it is known for TaSe₂. In both structures the germanium atoms are located in the empty octahedral positions of the van der Waals gap between the NbX₂ (X = S, Se) layers. Electron diffraction patterns from several Ge_xNbSe₂ crystal flakes show different superstructures and exhibit diffracted diffuse intensity: weak satellites corresponding to and 2a₀ × 2a₀ superstructures were observed for x ∼ 0.15 (a₀ is the basal lattice parameter of the host structure). For x ∼ 0.25-0.33, the same type of satellite is observed with a stronger intensity. For x ∼ 0.5 only satellites corresponding to the superstructure were present. In the case of Ge_xNbS₂, with 0.10 < x < 0.25, the germanium atoms are ordered in domains with an superstructure. In some crystals disorder along the c-axis has been observed.     

Enhanced characteristics of Ba5SmTi3Nb7O30 ferroelectric nanocrystalline ceramic prepared by mechanical activation process: A comparative study

In the present work, structural, dielectric, ferroelectric, piezoelectric and pyroelectric properties of tungsten-bronze structured Ba₅SmTi₃Nb₇O₃₀ ceramics, synthesized by mechanical activation and conventional solid-state reaction processes, have been studied with an objective of comparing the properties of the specimens synthesized by the two processes. X-ray diffraction analysis shows the formation of the compound in an orthorhombic structure by both the processes. Scanning electron microscopy reveals the formation of a fine granular microstructure in the specimen synthesized by mechanical activation process compared to the specimen synthesized by conventional solid-state method. The specimen prepared using mechanical activation process exhibits improved electrical properties with higher dielectric constant, lower dielectric loss and higher resistivity. The effective remanent polarization () value, d₃₃ value and pyroelectric coefficients are also observed to be higher in the sample synthesized by the mechanical activation process.