Re-examination of the crystal structure of Na2Al2B2O7: stacking faults and twinning

The crystal structure of the layered compound Na₂Al₂B₂O₇ is re-examined. It is found that stacking faults can be introduced easily in the sequence of [Al₂B₂O₇]_∞²⁻ lamellae. Both rotation and reflection twinning can form in the crystal by introducing appropriate stacking faults. A domain of the Sr₂Be₂B₂O₇-type structure might occur at the twin boundary. Single crystal refinement is performed successfully with the twinning model. A similar analysis and discussion is extended to the structures of Sr₂Be₂B₂O₇ and AEAl₂B₂O₇ (AE=Alkaline earth elements Ca, Sr and Ba).     

Synthesis crystal structure and ionic conductivity of Ca0.5Bi3V2O10 and Sr0.5Bi3V2O10

Two new compounds Ca_0.5Bi₃V₂O₁₀ and Sr_0.5Bi₃V₂O₁₀ have been synthesized in the ternary system: MO-Bi₂O₃-V₂O₅ system (M=M²⁺). The crystal structure of Sr_0.5Bi₃V₂O₁₀ has been determined from single crystal X-ray diffraction data, space group and Z=2, with cell parameters a=7.1453(3) Å, b=7.8921(3) Å, c=9.3297(3) Å, α=106.444(2)°, β=94.088(2)°, γ=112.445(2)°, V=456.72(4) Å³. Ca_0.5Bi₃V₂O₁₀ is isostructural with Sr_0.5Bi₃V₂O₁₀, with, a=7.0810(2) Å, b=7.8447(2) Å, c=9.3607(2) Å, α=106.202(1)°, β=94.572(1)°, γ=112.659(1)°, V=450.38(2) Å³ and its structure has been refined by Rietveld method using powder X-ray data. The crystal structure consists of infinite chains of (Bi₂O₂) along c-axis formed by linkage of BiO₈ and BiO₆ polyhedra interconnected by MO₈ polyhedra forming 2D layers in ac plane. The vanadate tetrahedra are sandwiched between these layers. Conductivity measurements give a maximum conductivity value of 4.54×10⁻⁵ and 3.63×10⁻⁵ S cm⁻¹ for Ca_0.5Bi₃V₂O₁₀ and Sr_0.5Bi₃V₂O₁₀, respectively at 725 °C.     

Syntheses, crystal structures and Si solubilities of new layered carbides Zr2Al4C5 and Zr3Al4C6

Two types of new ternary carbides, Zr₂Al₄C₅ and Zr₃Al₄C₆, have been synthesized and characterized by X-ray powder diffraction. The crystal structures were refined from laboratory X-ray powder diffraction data (CuKα₁) using the Rietveld method. These carbides form a homologous series with the general formula (ZrC)_mAl₄C₃ (m=2 and 3). The crystal structures can be regarded as intergrowth structures where the Al₄C₃-type [Al₄C₄] layers are the same, while the NaCl-type [Zr_mC_m+1] layers increase in thickness with increasing m value. The new carbides are most probably the end members of continuous solid-solutions (ZrC)_m[Al_4−xSi_x]C₃ with 0?x?0.44.     

X-ray powder diffraction studies and thermal behaviour of NaK2B9O15, Na(Na.17K.83)2B9O15, and (Na.80K.20)K2B9O15

The crystal structures of NaK₂B₉O₁₅ (, , , β=94.080(1)°, R_p=0.047, R_wp=0.059, R_B=0.026), Na(Na_.17K_.83)₂B₉O₁₅ (, , , β=94.228(2)°, R_p=0.053, R_wp=0.068, R_B=0.026), and (Na_.80K_.20)K₂B₉O₁₅ (, , , β=94.071(1)°, Z=4, R_p=0.041, R_wp=0.052, R_B=0.023) were refined in the monoclinic space groups P2₁/c(Z=4) using X-ray powder diffraction data and the Rietveld method. These nonaborates are isostructural to K₃B₉O₁₅. Their crystal structure consists of a three-dimensional open framework built up from three crystallographically independent triborate groups. The alkali metal cations are located on three different sites in the voids of the framework. High-temperature X-ray diffraction studies show that NaK₂B₉O₁₅ decomposes at about 700 °C in accordance with the peritectic reaction NaK₂B₉O₁₅↔K₅B₁₉O₃₁+liquid. The thermal expansion of NaK₂B₉O₁₅ and Na(Na_.17K_.83)₂B₉O₁₅ is highly anisotropic. A similarity of the thermal and compositional (Na-K substitution) deformations of NaK₂B₉O₁₅ is revealed: heating of NaK₂B₉O₁₅ by 1 °C leads to the same deformations of the crystal structure as increasing the amount of K atoms in (Na_1−xK_x)₃B₉O₁₅ by 0.04 at% K.     

Crystal structure of Ca12Al14O32Cl2 and luminescence properties of Ca12Al14O32Cl2:Eu

The crystal structure of Ca₁₂Al₁₄O₃₂Cl₂ was determined from laboratory X-ray powder diffraction data (CuKα₁) using the Rietveld method, with the anisotropic displacement parameters being assigned for all atoms. The crystal structure is cubic (space group , Z=2) with lattice dimensions a=1.200950(5) nm and V=1.73211(1) nm³. The reliability indices calculated from the Rietveld method were R_wp=8.48% (S=1.21), R_p=6.05%, R_B=1.27% and R_F=1.01%. The validity of the structural model was verified by the three-dimensional electron density distribution, the structural bias of which was reduced as much as possible using the maximum-entropy methods-based pattern fitting (MPF). The reliability indices calculated from the MPF were R_B=0.75% and R_F=0.56%. In the structural model there are one Ca site, two Al sites, two O sites and one Cl site. This compound is isomorphous with Ca₁₂Al_10.6Si_3.4O₃₂Cl_5.4. Europium-doped sample Ca₁₂Al₁₄O₃₂Cl₂:Eu²⁺ was prepared and the photoluminescence properties were presented. The excitation spectrum consisted of two wide bands, which were located at about 268 and 324 nm. The emission spectrum, when excited at 324 nm, resulted in indigo light with a peak at about 442 nm.     

Structural and magnetic characterisation of Aurivillius material Bi2Sr2Nb2.5Fe0.5O12

The n=3 Aurivillius material Bi₂Sr₂Nb_2.5Fe_0.5O₁₂ is investigated and combined structural refinements using neutron powder diffraction (NPD) and X-ray powder diffraction data (XRPD) data reveal that the material adopts a disordered, tetragonal (I4/mmm) structure at temperatures down to 2 K. Significant ordering of Fe³⁺ and Nb⁵⁺ over the two B sites is observed and possible driving forces for this ordering are discussed. Some disorder of Sr²⁺ and Bi³⁺ over the M and A sites is found and is consistent with relieving strain due to size mismatch. Highly anisotropic thermal parameters for some oxygen sites suggest that the local structure may be slightly distorted with some rotation of the octahedra. Magnetic measurements show that the material behaves as a Curie-Weiss paramagnet in the temperature range studied with no evidence of any long-range magnetic interactions. Solid solutions including Bi_3−xSr_xNb₂FeO₁₂, Bi₂Sr_2−xLa_xNb₂FeO₁₂ and Bi₂Sr₂Nb_3−xFe_xO₁₂ were investigated but single-phase materials were only successfully synthesised for a narrow composition range in the Bi₂Sr₂Nb_3−xFe_xO₁₂ system.     

Synthesis, crystal structure, and preliminary study of luminescent properties of InTbGe2O7

A new indium terbium germanate InTbGe₂O₇, which is a member of the thortveitite family, was prepared as a polycrystalline powder material by high-temperature solid-state reaction. This new compound crystallizes in the monoclinic system, space group C2/c (No. 15), with unit cell parameters a=6.8818(2) Å, b=8.8774(3) Å, c=9.7892(4) Å, β=101.401(1)°, V=586.25(4) ų and Z=4. Its structure was characterized by Rietveld refinement of powder laboratory X-ray diffraction data. It consists of octahedral sheets that are held together by sheets of isolated Ge₂O₇ diorthogroups composed of two tetrahedra sharing a common vertex. It contains only one octahedral site occupied by In³⁺ and Tb⁺³ cations. The characteristic mirror plane in the thortveitite (Sc₂Si₂O₇) space group (C2/m, No. 12) is not present in this new compound. Besides, in InTbGe₂O₇, the Ge–O–Ge angle bridging two diorthogroups is 156.8(2)° as compared to the one in thortveitite, which is 180°. On the other hand, luminescent properties were observed when it is excited with 376.5 nm wavelength. The luminescence spectrum shows typical transitions from the ⁵D₄ multiplet belonging to the trivalent terbium ion.     

Crystal structures of Rb2U2O7 and Rb8U9O31, a new layered rubidium uranate

Two alkali metal uranates Rb₂U₂O₇ and Rb₈U₉O₃₁ have been synthesized by solid state reaction at high temperature and their crystal structures determined from single crystal X-ray diffraction data, collected with a three circles Brucker SMART diffractometer equipped by Mo(Kα) radiation and a charge-coupled device (CCD) detector. Their structures were solved using direct methods and Fourier difference techniques and refined by a least-square method on the basis of F² for all unique reflections, with R₁=0.043 for 53 parameters and 746 independent reflections with I?2σ(I) for Rb₂U₂O₇, monoclinic symmetry, space group P2₁/c, , , , β=108.81(1)°, , , Z=2 and R₁=0.036 for 141 parameters and 2065 independent reflections with I?2σ(I) for Rb₈U₉O₃₁, orthorhombic, space group Pbna, , , , , , Z=4.The Rb₂U₂O₇ structure presents a strong analogy with that of K₂U₂O₇ and can be described by layers of distorted UO₂(O₄) octahedra built from dimeric units of edge shared octahedra further linked together by opposite corners. In Rb₈U₉O₃₁ puckered layers are formed by the association of two different uranium polyhedra, pentagonal bipyramids and distorted octahedra. The structure of Rb₈U₉O₃₁ is built from a regular succession of infinite ribbons similar to those observed in diuranates M₂U₂O₇ (MK, Rb) and infinite three polyhedra wide ribbons , to create an original undulated sheets .For both compounds Rb⁺ ions occupy the interlayer space and exhibit comparable mobility with conductivity measurements indicating an Arrhenius-type behavior.     

Crystal structure, thermal and magnetic properties of Cr2V4O13

Cr₂V₄O₁₃, a tetravanadate of Cr³⁺ has been prepared by repeated heating of stoichiometric amounts of Cr₂O₃ and V₂O₅ and its crystal structure is refined by Rietveld refinement of the powder XRD data. This compound crystallizes in a monoclinic lattice with unit cell parameters: a=8.2651(3), b=9.2997(3), c=14.5215(5) Å, β=102.618(3)°, V=1089.21(6) Å³ and Z=4 (Space group: P2₁/c). The U shaped (V₄O₁₃)⁶⁻ formed by corner connected VO₄ tetrahedra links the Cr₂O₁₀ (dimers of two edge shared CrO₆ octahedra) forming a three dimensional network structure of Cr₂V₄O₁₃. This compound is stable up to 635 °C and peritectically decomposes to orthorhombic CrVO₄ and V₂O₅ above this temperature. A possible long range antiferromagnetic ordering below 10 K is suggested from the squid magnetometry and electron paramagnetic resonance (epr) spectroscopic studies of Cr₂V₄O₁₃.     

Preparation, structure and photoluminescence properties of Eu and Ce-doped SrYSi4N7

Undoped and Eu²⁺ or Ce³⁺-doped SrYSi₄N₇ were synthesized by solid-state reaction method at 1400-1660 °C under nitrogen/hydrogen atmosphere. The crystal structure was refined from the X-ray powder diffraction data by the Rietveld method. SrYSi₄N₇ and EuYSi₄N₇, being isotypic with the family of compounds MYbSi₄N₇ (M=Sr, Eu, Ba) and BaYSi₄N_7, crystallize with the hexagonal symmetry: space group P6₃mc (No. 186), Z=2, a=6.0160 (1) Å, c=9.7894 (1) Å, V=306.83(3) Å³; and a=6.0123 (1) Å, c=9.7869 (1) Å, V=306.37(1) Å³, respectively. Photoluminescence properties have been studied for Sr_1−xEu_xYSi₄N₇ (x=0-1) and SrY_1−xCe_xSi₄N₇ (x=0-0.03) at room temperature. Eu²⁺-doped SrYSi₄N₇ shows a broad yellow emission band peaking around 548-570 nm, while Ce³⁺-doped SrYSi₄N₇ exhibits a blue emission band with a maximum at about 450 nm. SrYSi₄N₇:Eu²⁺ can be very well excited by 390 nm radiation, which makes this material attractive as conversion phosphor for LED lighting applications.     

Study of the cation distributions in Eu doped Sr2Y8(SiO4)6O2 by X-ray diffraction and photoluminescent spectra

The crystal structure and photoluminescent properties of europium doped silicate Sr₂Y₈(SiO₄)₆O₂:Eu³⁺ are reported. The Sr₂Y_8−xEu_x(SiO₄)₆O₂ compounds have typical apatite crystal structures with the P6₃/m space group. The distributions of Eu³⁺ between the two crystallographic sites 4f and 6h in the apatite structure are investigated by the powder X-ray diffraction and Rietveld refinement. Results show that Eu³⁺ ions only occupy the 4f sites when the Eu doping concentration is low (x=0-0.5 in Sr₂Y_8−xEu_x(SiO₄)₆O₂). However, in higher concentrations, Eu³⁺ ions begin to enter the 6h sites as well. The distributions of the Eu³⁺ are also reflected in photoluminescent spectra. The CIE coordinates for Sr₂Y₆Eu₂(SiO₄)₆O₂ are (0.63, 0.37), which is close to the pure red color.     

Structure of two new borates YCa3(AlO)3(BO3)4 and YCa3(GaO)3(BO3)4

By replacing Mn in YCa₃(MnO)₃(BO₃)₄ with trivalent Al and Ga, two new borates with the compositions of YCa₃(MO)₃(BO₃)₄ (M=Al, Ga) were prepared by solid-state reaction. Structure refinements from X-ray powder diffraction data revealed that both of them are isostructural to gaudefroyite with a hexagonal space group P6₃/m. Cell parameters of a=10.38775(13)Å, c=5.69198(10)Å for the Al-containing compound and a=10.5167(3)Å, c=5.8146(2)Å for the Ga analog were obtained from the refinements. The structure is constituted of AlO₆ or GaO₆ octahedral chains interconnected by BO₃ groups in the ab plane to form a Kagomé-type lattice, leaving trigonal and apatite-like tunnels. It is found that most rare-earth and Cr, Mn ions can be substituted into the Y³⁺ and M³⁺ sites, respectively, and the preference of rare-earth ions to locate in the trigonal tunnel is correlated to the sizes of the M³⁺ ions.     

Crystal structures of CsFe2S3 and RbFe2S3: synthetic analogs of rasvumite KFe2S3

The isostructural alkali thioferrate compounds CsFe₂S₃, RbFe₂S₃ and KFe₂S₃ have been synthesized by reacting Fe and S with their corresponding AFeS₂ (A=K, Rb, Cs) precursors. The crystal structures of these and binary compounds of intermediate composition were determined by Rietveld analysis of laboratory powder X-ray diffraction patterns. All of the synthesized compounds adopt the space group Cmcm (#63), Z=4 with: a=9.5193(8) Å, b=11.5826(10) Å, c=5.4820(4) Å for CsFe₂S₃; a=9.2202(7) Å, b=11.2429(9) Å, c=5.4450(3) Å for RbFe₂S₃; and a=9.0415(13) Å, b=11.0298(17) Å, c=5.4177(6) Å for KFe₂S₃. These mixed valence alkali thioferrates show regular changes in cell dimensions, AS₁₀ (A=K, Rb, Cs) polyhedron volumes, polyhedron distortion parameters, and calculated oxidation state of Fe with respect to increasing size of the alkali element cation. The calculated empirical oxidation state of iron varies from +2.618 (CsFe₂S₃), through +2.666 (RbFe₂S₃) to +2.77 (KFe₂S₃).     

Mechanochemical-thermal preparation and structural studies of mullite-type Bi2(GaxAl1−x)4O9 solid solutions

A series of Bi₂(Ga_xAl_1−x)₄O₉ solid solutions (0≤x≤1), prepared by mechanochemical processing of Bi₂O₃/Ga₂O₃/Al₂O₃ mixtures and subsequent annealing, was investigated by XRD, EDX, and ²⁷Al MAS NMR. The structure of the Bi₂(Ga_xAl_1−x)₄O₉ solid solutions is found to be orthorhombic, space group Pbam (No. 55). The lattice parameters of the Bi₂(Ga_xAl_1−x)₄O₉ series increase linearly with increasing gallium content. Rietveld refinement of the XRD data as well as the analysis of the ²⁷Al MAS NMR spectra show a preference of gallium cations for the tetrahedral sites in Bi₂(Ga_xAl_1−x)₄O₉. As a consequence, this leads to a far from random distribution of Al and Ga cations across the whole series of solid solutions.     

Low temperature phase transition studies on Pb(Mg0.5W0.5)O3 ceramic

We present here the results of X-ray diffraction (XRD), dielectric and calorimetric studies on lead magnesium tungustate, Pb(Mg_0.5W_0.5)O₃ (PMW) ceramic. It is shown that the low temperature antiferroelectric phase of PMW having orthorhombic structure (space group Pmcn) transforms to paraelectric cubic (space group Fm3m) phase at 281 K. The phase transition is of first order character as confirmed by coexistence of Pmcn and Fm3m phases over wide temperature range ∼50 K. The first order character of phase transition is also revealed by the observation of thermal hysteresis in the real part of dielectric permittivity and calorimetric studies. We do not find any evidence for the additional intermediate phase between antiferroelectric (Pmcn) and paraelectric (Fm3m) phases as reported in the literature. Anomalies in the heat flow and dielectric measurements support the finding of our XRD results and reveals that the phase transition temperature (T_c) is 281 K instead of 312 K reported in the literature.     

A structural study of the perovskite series Na0.75Ln0.25Ti0.5Nb0.5O3

The ternary stoichiometric perovskite compounds, Na_0.75Ln_0.25Ti_0.5Nb_0.5O₃ (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm) are intermediate members of the NaNbO₃-Na_0.5Ln_0.5TiO₃ solid solution series. The compounds were synthesized by standard ceramic methods at 1300 °C followed by annealing at 800 °C and quenching to ambient conditions. Rietveld analysis of the powder X-ray diffraction patterns shows that the compounds with Ln ranging from Pr to Tm adopt the orthorhombic space group Pbnm (a≈b≈√2a_p; c≈2a_p; Z=4) and the GdFeO₃ structure. In contrast, Na_0.75La_0.25Ti_0.5Nb_0.5O₃ adopts the orthorhombic space group Cmcm (a≈b≈c≈2a_p; Z=4). All cations located at the A- and B-sites are disordered in these compounds. The unit cell parameters and cell volumes of the compounds decrease regularly with increasing atomic number of the Ln cation. The Pbnm compounds with Ln from Sm to Tm have A-site cations in eight-fold coordination. A-site cations in the Pr and Nd compounds are considered to be in ten-fold coordination. Analysis of the crystal chemistry of the Pbnm compounds shows that B-site cations enter the second coordination sphere of the A-site cations for compounds with Ln from Tb to Tm as the A-B intercation distances are less than the maximum A-^IIO(2) bond lengths. The [111] tilt angles of the (Ti,Nb)O₆ polyhedra in the Pbnm compounds increase with increasing atomic number from 11.1° to 15.8° and are less than those observed in lanthanide orthoferrite and orthoscandate perovskites. These data are considered as relevant to the sequestration of lanthanide fission products in perovskite and the structure of lanthanide-bearing perovskite-structured minerals.     

The crystal structure of synthetic simmonsite, Na2LiAlF6

The structure of the synthetic fluoroperovskite, Na₂LiAlF₆ (simmonsite), has been determined by powder X-ray diffraction using the Rietveld method of structure refinement. The compound adopts space group P2₁/n [#14; a=5.2842(1); b=5.3698(1); c=7.5063(2)Å; β=89.98(1)°; Z=4), and is a member of the cryolite (Na₂NaAlF₆) structural group characterized by ordering of the B-site cations (Li, Al) and tilting of the BF₆ octahedra according to the tilt scheme a⁻b⁻c⁺. Rotations of the B-site polyhedra are less (Φ_Li=14.9°; Φ_Al=17.0°) than those found in cryolite (Φ_Na=18.6; Φ_Al=23.5°) because of the larger difference in the ionic radii of the B-site cations in cryolite as compared to those in simmonsite. Na at the A-site is displaced from the special position resulting in 10- and 8-fold coordination in simmonsite and cryolite, respectively. By analogy with the synthetic compound, naturally occurring simmonsite is considered to adopt space group P2₁/n (#14) and not the P2₁(#4) or P2₁/m(#11) space groups.     

A new promising scintillator Ba3InB9O18

We report on the synthesis, crystal structure and scintillation property of a new compound Ba₃InB₉O₁₈. This compound crystallizes in space group P6₃/m with unit cell of dimensions a=7.1359(3) Å, c=16.6151(8) Å and V=732.697 Å³ with two Ba₃InB₉O₁₈ molecular formula. Its crystal structure is made up of planar B₃O₆ groups parallel to each other along the 〈0001〉 direction, regular InO₆ octahedra, irregular BaO₆ hexagons and BaO₉ polyhedra to form an analog structure of Ba₃YB₉O₁₈. DTA and TGA curves for Ba₃InB₉O₁₈ show that it is a chemically stable and congruent melting compound. Its X-ray excited luminescence spectra show an intense emission band in the range of 360-500 nm with a maximum at 400 nm. Light yield for Ba₃InB₉O₁₈ is about 75% as large as that for BGO under the same measurement conditions. There may exist a correlation between the scintillation properties and the crystal structural features of Ba₃InB₉O₁₈.     

Crystal Structure of SrAl2B2O7 and Eu Luminescence

The crystal structure of strontium dialuminodiborate SrAl₂B₂O₇ has been established by single-crystal X-ray diffraction methods. The compound crystallizes in the trigonal system (space group R c, Z=6) with cell parameters a=4.893(1) Å and c=47.78(1) Å. Aluminium and boron atoms are, respectively, in tetrahedral and triangular oxygen coordination. The assembly of Al₂O₇ units and BO₃ triangles forms double layers between which Sr²⁺ ions are located. The Eu²⁺-doped crystalline powder exhibits a luminescence band with maximum at 415 nm. Luminescence characteristics are compared to those of other strontium borates.     

A mixed cation nickel diphosphate with a layered intergrowth structure: synthesis, structural and magnetic characterization of Na(NH4)[Ni3(P2O7)2(H2O)2]

A nickel diphosphate with mixed cations, Na(NH₄)[Ni₃(P₂O₇)₂(H₂O)₂] with a layered structure has been synthesized under hydrothermal conditions for the first time and characterized by single crystal X-ray diffraction, IR spectroscope and magnetization measurements. The structure consists of cis- and trans-edge sharing NiO₆ octahedral chains linked via P₂O₇ units to [Ni₃P₄O₁₆]²⁻ layers. The ammonium and sodium cations are alternately located in the interlayer spaces. The mixed cations play an important role in the structural formation of this layered compound, leading to a new layer-stacking variant. The magnetic susceptibility obeys a Curie–Weiss law with μ_eff of 3.32 μ_B, showing the Ni²⁺ character and weak antiferromagnetic interactions.