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.     

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.     

Crystal structure of a new organic dihydrogenomonophosphate (C6H8N3O)2(H2PO4)2

Chemical preparation, X-ray single-crystal, thermal behavior, and IR spectroscopy investigations are given for a new organic cation dihydrogenomonophosphate (C₆H₈N₃O)₂(H₂PO₄)₂ (denoted IAHP) in the solid state. This compound crystallizes in the orthorhombic space group P2₁2₁2₁. The unit cell dimensions are: a = 7.422(3) Å, b = 12.568(5) Å, c = 20.059(8) Å with V = 1871.1(13) Å³ and Z = 4. The structure has been solved using direct method and refined to a reliability R factor of 0.029. The atomic arrangement can be described as inorganic layers of H₂PO₄⁻ anions between which are located the organic groups (C₆H₈N₃O)⁺ through multiple hydrogen bonds.     

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.     

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).     

Synthesis and crystal structures of a new (2,3-(CH3)2C6H3NH3)H2XO4 (X=P,As)

The aim of encapsulation of 2,3-dimethylanilinium cation in (H₂XO₄)_n polymeric anion chains is to build acentric frameworks that are efficient for non-linear optical (NLO) applications. The synthesis and structures of two new inorganic–organic NLO crystals with general formula (2,3-(CH₃)₂C₆H₃NH₃)H₂XO₄ (X=P, As) are reported. The magnitude of their second harmonic generations (SHG) responses was found to be between the KDP and urea. They crystallize with monoclinic unit-cells and are isotopic. We have determined the structure of phosphoric salt. The following unit-cell parameters were found: a=8.866(3) Å, b=5.909(6) Å, c=10.644(5) Å, β=112.44(1)°, V=515.5(5) Å³ and D_X=1.412 g cm⁻³. The space group is P2₁ with Z=2. The structure was refined with R=0.041 (R_w=0.057) for 1652 reflections with I≥3σ(I). It exhibits infinite (H₂PO₄)_nⁿ⁻ chains. The organic groups (2,3-(CH₃)₂C₆H₃NH₃)⁺ are anchored between adjacent polyanions through multiple hydrogen bonds. Chemical preparation, crystal structure, calorimetric and spectroscopic investigation are described.     

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.     

Structure and magnetism in Pr3RuO7

The crystal structure of the ordered fluorite, Pr₃RuO₇, was refined from powder neutron diffraction data in Cmcm. An interesting structural feature is the presence of relatively well separated zig-zag chains of corner sharing RuO₆ octahedra, Ru–Ru interchain distance 6.61 Å vs. Ru–Ru intrachain distance of 3.76 Å. Magnetic susceptibility data show a Curie–Weiss behavior for T>225 K with C=5.96(4) emu K mol⁻¹ and θ_c=+11(2) K. In an attempt to separate the contributions of Pr(3+) and Ru(5+), the properties of isostructural Pr₃TaO₇ were also measured, yielding C=4.63(3) emu K mol⁻¹. Thus, the contribution of Ru(5+), 4d³, S=3/2, to the measured Curie constant is estimated to be 1.33 emu K mol⁻¹, not far from the spin-only value of 1.87 emu K mol⁻¹. This supports the view that the Ru 4d electrons are localized and magnetic, not itinerant. A susceptibility maximum at about 50 K is attributed to long-range magnetic order and this is substantiated by neutron diffraction data. There is little evidence for one-dimensional antiferromagnetic correlations in this material but behavior characteristic of short-range ferromagnetic correlations attributed to Pr–Ru exchange interactions are found in the temperature range 50–200 K, consistent with the positive θ_c.     

Two 2-D 36 tessellated metal–organic frameworks constructed from trimetallic clusters and dicarboxylate ditopic links

Two metal–organic framework compounds, [Zn₃(1,4-BDC)₃(Py)₂]·2(1,4-dioxane) (MOF-CJ6) and [Cd₃(bpdc)₃(H₂O)₂] (MOF-CJ7), have been solvothermally synthesized and characterized by single crystal X-ray diffraction, X-ray powder diffraction, ICP, IR and photoluminescence spectroscopy analyses, respectively. MOF-CJ6 crystallizes in monoclinic, space group P2(1)/n (no. 14) with a = 14.6886(14) Å, b = 9.6194(6) Å, c = 15.9161(16) Å and β = 105.687(6)°. Its framework can be described as a 2-D 3⁶ tessellated net based on the assembly of trimeric Zn₃(CO₂)₆ clusters and 1,4-benzenedicarboxylates ditopic links. The 2-D nets can be further linked into a novel 3-D supramolecular hexagonal lattice (hex) network through π–π packing interaction. MOF-CJ7 crystallizes in trigonal, space group R-3 (no. 148) with a = 14.1129(8) Å, b = 14.1129(8) Å, c = 20.1168(13) Å and γ = 120°. MOF-CJ7 exhibits analogous framework topology with that of MOF-CJ6, consisting of trimeric Cd₃(CO₂)₆ clusters and 4,4′-biphenyldicarboxylate links.     

X-ray powder diffraction,vibration and thermal studies of [A0.92(NH4)0.08]2TeCl4Br2 with A = Cs,Rb: Influence of mixed cationic and anionic substitutions

The crystal structures of [A_0.92(NH₄)_0.08]₂TeCl₄Br₂ with A = Cs, Rb have been determined using X-ray powder diffraction techniques. The two compounds crystallize in the tetragonal space group P4/mnc, with the unit cell parameters: a = 7.452(1) Å, c = 10.544(3) Å, Z = 2 and a = 7.315(2) Å, c = 10.354(4) Å, Z = 2 in the presence of Cs and Rb, respectively. These two compounds have an antifluorite-type arrangement of NH₄⁺/Rb⁺/Cs⁺ and octahedral TeCl₄Br₂^2? anions. The stability of these structure is by ionic and hydrogen bonding contacts: A?Cl, A?Br and N–H?Cl, N–H?Br. The different vibrational modes of these powders were analysed by FTIR and Raman spectroscopic studies. A DTA/TGA experiment reveals one endothermic peak at 780 K implicating the decomposition of the sample. At low temperature, one endothermic peak in thermal behavior is detected at around 213 K by DSC experiment. This transition was confirmed by dielectric measurements.     

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.     

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 and tunable luminescence of RbCaGd(PO4)2:Ce3+, Mn2+ phosphors

RbCaGd(PO₄)₂ doped with Ce³⁺, Mn²⁺ was synthesized by the sol-gel method. The crystal structure and crystallographic location of Ce³⁺ in RbCaGd(PO₄)₂ were identified by Rietveld refinement. Powder X-ray diffraction (XRD) revealed that the structure of RbCaGd(PO₄)₂:Ce³⁺ compounds is hexagonal structure which is similar to that of hexagonal LnPO₄ with the lattice constant of a = b = 7.005(57) Å, c = 6.352(05) Å, and V (cell volume) = 269.980 Å³. The photoluminescence behavior and emission mechanism were studied systematically by doping activators in the RbCaGd(PO₄)₂ host. The Mn²⁺ incorporated RbCaGd(PO₄)₂:Ce³⁺, Mn²⁺ compounds exhibited blue emission from the parity- and spin-allowed f-d transition of Ce³⁺ and orange-to-red emission from the forbidden ⁴T₁ → ⁶A₁ transition of Mn²⁺. The emission chromaticity coordinates of RbCaGd(PO₄)₂:0.10Ce³⁺, xMn²⁺ (x = 0.16, 0.25) are close to the white region due to an energy transfer process and the energy transfer mechanism from Ce³⁺ to Mn²⁺ in the RbCaGd(PO₄)₂ host was dominated by dipole-dipole interactions.     

Synthesis,crystal structure and properties of a new lead fluoride borate,Pb3OBO3F

A new compound, Pb₃OBO₃F, has been grown by the high temperature solution method from the PbO–PbF₂–B₂O₃ system. It crystallizes in the orthorhombic system, space group Pbcm with unit-cell parameters a = 7.6313(14) Å, b = 6.5229(12) Å, c = 11.906(2) Å, Z = 4, volume = 592.66(19) Å³. The structure of the compound is solved by the direct methods and refined to R₁ = 0.0528 and wR₂ = 0.1400. Pb₃OBO₃F consists of Pb(1)O₃F tetrahedra, Pb(2)O₄ tetrahedra and BO₃ triangles which build up the symmetrical chains extended along the c-axis. The powder X-ray diffraction pattern of the Pb₃OBO₃F has been measured. Functional groups presented in the sample were identified by Fourier transform infrared spectrum.     

Anisotropic thermal expansion behavior in tetragonal Sr2MgWO6

The colorless sample of Sr₂MgWO₆ was prepared by conventional solid-state reaction of stoichiometric amounts of SrCO₃, WO₃ and MgO and characterized by powder X-ray diffraction (XRD) studies. In the temperature range of 300–15 K, detailed structural studies on Sr₂MgWO₆ were carried out by Rietveld refinements of the observed powder neutron diffraction (ND) data. At ambient temperature Sr₂MgWO₆ crystallizes in tetragonal (space group I4/m) lattice with unit cell parameters: a = 5.5882(2) and c = 7.9452(7) Å, V = 248.11(3) Å³, Z = 2. This tetragonal (I4/m) structure is retained down to 15 K. The structural analysis of the sample at different temperatures indicates no appreciable change in the MgO and WO bond lengths. However, a decrease in the tilt angle is observed with increasing temperature. The negative thermal expansion of the c-axis is attributed to increasing transverse displacement amplitude of the bridging oxygen atoms along this axis.     

Magnetic properties of nanosized Sr2CrReO6 powders prepared by a combustion synthesis process

Double perovskite, Sr₂CrReO₆, nanoparticles in the size range 10–25 nm have been prepared by a combustion method. Its coercivity (H_c) at 5 and 300 K are determined to be 16.1 and 6.5 kOe, respectively. Using the law of approach to saturation, the obtained saturation magnetization σ_s (5 K) and σ_s (300 K) are 0.41 and 0.32 μB per formula unit (f.u.), respectively. The values of saturation magnetization are lower than the expected value 1 μB/f.u. considering the antiferromagnetic coupling between Cr³⁺ (3d³, S = 3 / 2) and Re⁵⁺ (5d², S = 1). At the same time high field irreversibility in M(H) curves and zero field cooled–field cooled (ZFC–FC) processes has also been found. A field-cooled (FC) hysteresis loop shift decreases with increasing temperature and vanishes near 350 K. It is suggested that the observed reduction of σ_s and shifted hysteresis loops are caused by the exchange interaction between the ferromagnetic core of the Sr₂CrReO₆ nanoparticles and its surface layer with disordered spins.     

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.     

First observation of the reversible O3 ↔ P2 phase transition: Crystal structure of the quenched high-temperature phase Na0.74Ni0.58Sb0.42O2

According to thermal expansion data, O3-type phase Na_xNi_(1+x)/3Sb_(2−x)/3O₂ (x ≈ 0.8) undergoes at ca. 1270 K a reversible transition to a less dense form. The high-temperature phase quenched to liquid nitrogen belongs to P2 type, space group P6₃/mmc (no. 194), a = 3.0123 Å(2), c = 11.2264 Å(7) for x ≈ 0.74 at 298 K. The stabilisation of P2 versus O3-type structure at high temperatures seems to be due to alkali distribution over greater number of sites thus increasing entropy and decreasing Na⁺–Na⁺ repulsion.     

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.