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.     

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.     

Synthesis and crystal structure of a novel lithium bismuth phosphate, Li2Bi14.67(PO4)6O14

A lithium bismuth phosphate, Li₂Bi_14.67(PO₄)₆O₁₄, has been synthesized for the first time by the solid-state method. The crystal structure was determined by single crystal X-ray diffraction at 150 K. Li₂Bi_14.67(PO₄)₆O₁₄ crystallizes in the monoclinic system C2/c (No. 15), with a = 30.8189(4) Å, b = 5.2691(3) Å, c = 24.5302(3) Å, β = 122.84(2)°, V = 3346.81(1) Å³ and Z = 2. The structure along the b axis consists of layers of [Bi₂O₂] units as the basic building block. These are separated by isolated PO₄ and LiO₄ tetrahedra. The oxygen co-ordination around two of the phosphorus atoms is disordered. Solid-state ⁷Li NMR studies confirm the presence of lithium in the structure. The material shows ionic conductivity of the order of 10⁻⁵ S cm⁻¹ at 600 °C.     

M2Y8(SiO4)6O2: Tb (M = Ca, Sr) phosphors: Sol-gel synthesis from N-2-aminoethylic-3-aminopropyldiethoxysilane and different photoluminescence behavior

M₂Y₈(SiO₄)₆O₂: Tb³⁺ (M = Ca, Sr) phosphors have been synthesized with a new silicon source silane crosslinking reagent (N-2-aminoethylic-3-aminopropyldiethoxysilane [NH₂(CH₂)₂NH(CH₂)₃SiCH₃(OCH₃)₂], abbreviated as AEAPMMS) through the sol-gel process, both of which present the characteristic emission ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) of Tb³⁺ ions. It is interesting to be found that the high energy level blue emission (⁵D₃ → ⁷F_J (J = 6, 5, 4, 3) transition) still can be found in the emission spectrum of Ca₂Y₈(SiO₄)₆O₂: Tb³⁺ while it disappears in the emission spectrum of Sr₂Y₈(SiO₄)₆O₂: Tb³⁺ for the cross-relaxation-induced quenching.     

Effect of doping with Nd ions on the structural and ferroelectric properties of Ca0.28Ba0.72Nb2O6 single crystal

The crystal structure of Ca_0.28Ba_0.72Nb₂O₆ (CBN-28) crystal with Nd-doping has been determined from X-ray single crystal diffraction data, in the tetragonal system with space group P4bm and the following parameters: a = b = 12.458 Å, c = 3.954 Å, V = 613.688 Å³, and Z = 5. X-ray diffraction results on a Nd-doped CBN-28 single crystal also have demonstrated that Nd³⁺ and Ca²⁺ occupy the same site in the crystal structure. Dielectric and ferroelectric measurements have been performed. Transition from ferroelectric to paraelectric at around 223 °C has been observed. The Nd-doped crystal has a lower Curie temperature (T_m) than that of undoped CBN-28 crystal. The spontaneous polarization (P_s) and coercive electric field (E_c) also decrease compared with their values in the undoped CBN-28 crystal.     

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).     

Novel Dy-doped Ca2Gd8(SiO4)6O2 white light phosphors for Hg-free lamps application

The luminescent properties of Ca₂Gd_8(1−x)(SiO₄)₆O₂:xDy³⁺ (1% ≤ x ≤ 5%) powder crystals with oxyapatite structure were investigated under vacuum ultraviolet excitation. In the excitation spectrum, the peaks at 166 nm and 191 nm of the vacuum ultraviolet region can be assigned to the O²⁻ → Gd³⁺, and O²⁻ → Dy³⁺ charge transfer band respectively, which is consistent with the theoretical calculated value using Jφrgensen's empirical formula. While the peaks at 183 nm and 289 nm are attributed to the f-d spin-allowed transitions and the f-d spin-forbidden transitions of Dy³⁺ in the host lattice with Dorenbos's expression. According to the emission spectra, all the samples exhibited excellent white emission under 172 nm excitation and the best calculated chromaticity coordinate was 0.335, 0.338, which indicates that the Ca₂Gd₈(SiO₄)₆O₂:Dy³⁺ phosphor could be considered as a potential candidate for Hg-free lamps application.     

Synthesis and crystal structure of triphosphate RbPrHP3O10

Crystals of RbPrHP₃O₁₀ have been grown by the flux technique and characterized by single-crystal X-ray diffraction. RbPrHP₃O₁₀ crystallizes in the triclinic space group with lattice parameters: a = 7.0655(5), b = 7.7791(4), c = 8.6828(6) Å, α = 74.074(3), β = 74.270(3), γ = 82.865(2)°, V = 441.09(5) ų, Z = 2. The crystal structure has been solved yielding a final R(F²) = 0.0443 and R_w(F²) = 0.1426 for 1955 independent reflections (F_o² ≥ 2σ(F_o²)). The structure of RbPrHP₃O₁₀ consists of PrO₈ polyhedra and P₃O₁₀⁵⁻ groups sharing oxygen atoms to form a two-dimensional framework; the PrO₈ polyhedra form infinite chains by edge-sharing. Each Rb⁺ ion is bonded to 10 oxygen atoms, these ions are located between chains formed of (HP₃O₁₀)⁴⁻. The energies of the vibrational modes of the crystal were obtained from measurements of the infrared spectrum.     

Synthesis and characterization of K2NiF4-type CaLnCoO4 (Ln = Sm and Gd)

K₂NiF₄-type CaLnCoO₄ (Ln = Sm and Gd) has been synthesized at 1173 or 1223 K in air using citric acid (CA) and ethylene glycol (EG). CaLnCoO₄ (Ln = Sm and Gd) has an orthorhombic structure with the space group Bmab. The average particle sizes are approximately 300 nm for CaSmCoO₄ and approximately 170 nm for CaGdCoO₄, respectively. The global instability index (GII) indicates that the crystal structure of CaGdCoO₄ is more stable than that of CaSmCoO₄. CaLnCoO₄ (Ln = Sm and Gd) is a p-type semiconductor and shows paramagnetic behavior above 5 K. The 1/χ-T curve of CaSmCoO₄ deviates from the Curie-Weiss law, whereas the 1/χ-T curve of CaGdCoO₄ follows the Curie-Weiss law in the temperature range of 5 ≤ T ≤ 300 K. From the values of the observed effective magnetic moment (μ_eff) of CaLnCoO₄ (Ln = Sm and Gd), it is considered that the spin state of the Co³⁺ ion is low.     

Controllable synthesis and magnetic property of BiMn2O5 crystals

Uniform submicron BiMn₂O₅ particles were prepared via a facile one-step hydrothermal route at low temperature. Bi(NO₃)₃, MnCl₂·4H₂O and KMnO₄ were used as starting materials; KOH as a pH adjustor and also as a mineralizer. Single-crystalline orthorhombic BiMn₂O₅ sample with controllable morphology was obtained. The microstructure strongly depends on the molar ratio of the starting materials, KOH concentration and reaction temperature. X-ray photoelectron spectroscopy shows the existence of Mn⁴⁺ state. Magnetic measurement indicates Néel temperature T_N at 44 K. The susceptibility above T_N obeys the Curie-Weiss law, χ = C/(T − θ), with θ = −350 K. The effective paramagnetic moment μ_eff = 4.66 μ_B/Mn, demonstrating the coexistence of mixed Mn³⁺ and Mn⁴⁺ valences.     

Synthesis and characterization of a new organic dihydrogen phosphate-arsenate: [H2(C4H10N2)][H2(As, P)O4]2

Chemical preparation, crystal structure, calorimetric and spectroscopic investigations (IR and RMN) are given for a new non-centrosymmetric organic-cation dihydrogen phosphate-arsenate [H₂(C₄H₁₀N₂)][H₂(As, P)O₄]₂. This compound is triclinic P1 with the following unit-cell parameters: a = 7.082(2) Å, b = 7.796(1) Å, c = 12.05(3) Å, α = 95.37(2)°, β = 98.38(3)°, γ = 62.98(1)°, Z = 2, V = 586.2(1) Å³ and D_x = 1.836 g cm⁻³. The crystal structure has been solved and refined to R = 0.03 using 2328 independent reflections. The structure can be described as infinite (H₂XO)_n chains spreading parallel to the b direction. These chains are themselves interconnected by a set of NH?O hydrogen bonds generated by the organic entities, alternating with the chains. Solid-state ¹³C, ¹⁵N and ³¹P MAS NMR spectroscopies are in agreement with the X-ray structure.     

Synthesis, structure refinement and characterisation of a new oxyphosphate Mg0.50TiO(PO4)

A new titanium oxyphosphate Mg_0.50TiO(PO₄) has been synthesized and characterized by several physical techniques: X-ray diffraction, ³¹P MAS-NMR, Raman diffusion, infrared absorption and diffuse reflectance spectroscopy. It crystallizes in the monoclinic system with unit cell parameters: a = 7.367(9), b = 7.385(8), c = 7.373(9) Å, β = 120.23(1), with the space group P2₁/c (no. 14), Z = 4. The crystal structure has been refined by the Rietveld method using X-ray powder diffraction. The conventional R indices obtained are R_wp = 0.138, R_p = 0.096 and R_B = 0.0459. The structure of Mg_0.50TiO(PO₄) consists of infinite chains of corner-shared [TiO₆] octahedra parallel to the c-axis, crosslinked by corner-shared [PO₄] tetrahedra. These infinite chains have alternating short (1.74 Å) and long (2.26 Å) TiO bonds and are similar to those found in titanium oxyphosphate M^II_0.50TiO(PO₄) (M²⁺ = Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺). The magnesium atom is located in an antiprism between two [TiO₆] octahedra. ³¹P MAS NMR showed only a single ³¹P resonance line, in a good agreement with the crystal structure. Raman and IR spectra show strong bands respectively at 765 and 815 cm⁻¹, attributed to the vibration of TiOTiO bonds in the infinite chains. The gap due to the Oxygen-Titanium(IV) charge transfer is 3.37 eV.     

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 structure and properties of the new complex vanadium oxide K2SrV3O9

The new complex vanadium oxide K₂SrV₃O₉ has been synthesized and investigated by means of X-ray powder diffraction (XPD), electron microscopy and magnetic susceptibility measurements. The oxide has an orthorhombic unit cell with lattice parameters a = 10.1922(2) Å, b = 5.4171(1) Å, c = 16.1425(3) Å, space group Pnma and Z = 4. The crystal structure of K₂SrV₃O₉ has been refined by Rietveld method using X-ray powder diffraction data. The structure contains infinite chains built by V⁴⁺O₅ square pyramids linked to each other via VO₄ tetrahedra. The chains form layers and potassium and strontium cations orderly occupy structural interstices between these layers. Electron diffraction as well as high resolution electron microscopy confirmed the structure solution. Magnetic susceptibility measurements revealed an antiferromagnetic interaction with J of the order of 100 K inside the chains and no long-range magnetic order above 2 K. The origin of the magnetic exchange is likely a result of super-exchange interaction through the two VO₄ tetrahedra linking the polyhedra with the magnetic V⁴⁺ cations.     

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.     

Synthesis and crystal structure of Cu2NiO(B2O5) and Cu2MgO(B2O5)

A transport reaction synthesis technique has been used to prepare single crystals of two pyroborate compounds having the formulas Cu₂NiO(B₂O₅) and Cu₂MgO(B₂O₅). The two compounds are isostructural and crystallize in the monoclinic space group P2₁/c. Cu₂NiO(B₂O₅): a=3.2003(10), b=14.775(3), c=9.097(3), β=93.28(4), V=429.4(2) Å³, Z=4; and Cu₂MgO(B₂O₅): a=3.2401(6), b=14.790(2), c=9.147(2), β=94.88(2), V=436.7(2) Å³, Z=4. The structures of Cu₂NiO(B₂O₅) and Cu₂MgO(B₂O₅) were, respectively, refined from 804 and 1000 independent reflections to the final residuals R1=0.0366, wR2=0.0911 and R1=0.0231, wR2=0.0644. Both compounds exhibit a chevron-like structure built up of ribbons, made of edge-connected copper and nickel-oxygen polyhedra, running along the (1 0 0) direction. These ribbons are connected from one another via oxygen atoms and the cohesion of the three-dimensional network is ensured by [B₂O₅] entities. Cu in part occupies the position for Ni or Mg, so that the compounds actually are solid solution compounds. Ni or Mg atoms are octahedrally coordinated by oxygen, while the two pure Cu sites show [4] and [4+1] coordination, for Cu(1) and Cu(2), respectively. The ELNES B-K edge spectra for the two compounds support that the borate group present is [B₂O₅].     

Preparation and crystal structure of a new tin titanate containing Sn; Sn2TiO4

Single crystals of a new tin titanate containing Sn²⁺, Sn₂TiO₄ was prepared by high temperature reaction in an evacuated quartz tube and its crystal structure was determined by single crystal X-ray diffraction data. The tin titanate crystallizes in the tetragonal space group P4₂/mbc with a = 8.490(2) and c = 5.923(3) Å, Z = 4 and the final R factors are R = 0.0497 and R_w = 0.0676 for 354 unique reflections. This tin titanate is isostructural with the low temperature form of Pb₃O₄(Pb₂²⁺Pb⁴⁺O₄). This compound was oxidized above 600 °C accompanying the mass gain and finally changed to rutile-type solid solution (Sn,Ti)O₂.     

Thermal, spectroscopic and magnetic properties of the CoxNi1−x(SeO3)·2H2O (x = 0, 0.4, 1) phases: Crystal structure of Co0.4Ni0.6(SeO3)·2H2O

The Co_xNi_1−x(SeO₃)·2H₂O (x = 0, 0.4, 1) family of compounds has been hydrothermally synthesized under autogeneous pressure and characterized by elemental analysis, infrared and UV-vis spectroscopies and thermogravimetric and thermodiffractometric techniques. The crystal structure of Co_0.4Ni_0.6(SeO₃)·2H₂O has been solved from single-crystal X-ray diffraction data. This phase is isostructural with the M(SeO₃)·2H₂O (M = Co and Ni) minerals and crystallizes in the P2₁/n space group, with a = 6.4681(7), b = 8.7816(7), c = 7.5668(7) Å, β = 98.927(9)° and Z = 4. The crystal structure of this series of compounds consists of a three-dimensional framework formed by (SeO₃)²⁻ selenite oxoanions and edge-sharing M₂O₁₀ dimeric octahedra in which the metallic cations are coordinated by the oxygens belonging to both the selenite groups and water molecules. The diffuse reflectance spectra show the essential characteristics of Co(II) and Ni(II) cations in slightly distorted octahedral environments. The calculated values of the Dq and Racah (B and C) parameters are those habitually found for the 3d⁷ and 3d⁸ cations in octahedral coordination. The magnetic measurements indicate the existence of antiferromagnetic interactions in all the compounds. The magnetic exchange pathways involve the metal orbitals from edge-sharing dimeric octahedra and the (SeO₃)²⁻ anions which are linked to the M₂O₁₀ polyhedra in three dimensions.     

Crystal structure and ionic conductivity of ruthenium diphosphate ARu2(P2O7)2, A=Li, Na, and Ag, with a tunnel structure

Crystal structure and ionic conductivity of ruthenium diphosphates, ARu₂(P₂O₇)₂ A=Li, Na, and Ag, were investigated. The structure of the Ag compound was determined by single crystal X-ray diffraction techniques. It crystallized in the triclinic space group P−1 with a=4.759(2) Å, b=6.843(2) Å, c=8.063(1) Å, α=90.44(2)°, β=92.80(2)°, γ=104.88(2)°, V=253.4(1) Å³. The host structure of it was composed of RuO₆ and P₂O₇ groups and formed tunnels running along the a-axis, in which Ag⁺ ions were situated. The ionic conductivities have been measured on pellets of the polycrystalline powders. The Li and Ag compounds showed the conductivities of 1.0×10⁻⁴ and 3.5×10⁻⁵ S cm⁻¹ at 150 °C, respectively. Magnetic susceptibility measurement of the Ag compound showed that it did not obey the Curie-Weiss law and the effective magnetic moment decreased as temperature decreased due to the large spin-orbital coupling effect of Ru⁴⁺ ions.