The synthesis and structure of alkaline earth and cerium (IV) phosphates (Ce,B, □)[PO<Subscript>4</Subscript>] (<Emphasis Type="Italic">B</Emphasis> = Mg,Ca)

Double orthophosphates (Ce(IV), B, □)[PO₄] (B = Mg, Ca) were obtained after thermal treatment of gels with stoichiometric contents of components. The compounds obtained were characterized by X-ray diffraction analysis, infrared spectroscopy, and the electron spin resonance technique. The crystal structures were refined by the Rietveld method within the sp. gr. P2₁/n. The refinement was performed in the anisotropic approximation of atomic displacements for cations and isotropic approximation for oxygen.     

Structural transformations in Cu<Subscript>1.95</Subscript>Ni<Subscript>0.05</Subscript>S crystals

A solid solution of the Cu_1.95Ni_0.05S composition has been synthesized for the first time due to the partial replacement of Cu with Ni atoms in Cu₂S. The polymorphic transformations in the polycrystalline samples in the temperature range of 300–1400 K have been investigated by X-ray diffraction and differential thermal analysis. It is established that, at room temperature, the synthesized Cu_1.95Ni_0.05S samples have an orthorhombic lattice with unit-cell parameters a = 26.50 Å, b = 15.39 Å, and c = 13.85 Å (sp. gr. Abm2). Heating to T = 379 ± 2 K leads to its transformation into a hexagonal lattice with parameters a = 3.960 Å and c = 6.78 Å (sp. gr. P6₃/mmc). At 750 ± 2 K, the hexagonal modification is transformed into a cubic one with period a = 5.788 Å (sp. gr. Fm\(\bar 3\)m). The phase transition in this crystal is enantiotropic.     

Crystal structure and microtwinning of monoclinic La<Subscript>3</Subscript>SbZn<Subscript>3</Subscript>Ge<Subscript>2</Subscript>O<Subscript>14</Subscript> crystals of the langasite family

The crystal structure of monoclinic La₃SbZn₃Ge₂O₁₄ crystals from the langasite family is determined by X-ray diffraction analysis [a = 5.202(1) Å, b = 8.312(1) Å, c = 14.394(2) Å, β = 90.02(1)°, sp. gr. A2, Z = 2, and R/R _w = (5.2/4.6)%]. The structure is a derivative of the Ca₃Ga₂Ge₄O₁₄-type structure (a = 8.069 Å, c = 4.967 Å, sp. gr. P321, Z = 1). The crystal studied is a polysynthetic twin with the twin index n = 2, whose monoclinic components are related by pseudomerohedry by a threefold rotation axis of the supergroup P321.     

On the structural basis of the presence of two optical axes in α-HIO<Subscript>3</Subscript> crystal

An X-ray diffraction study of α-HIO₃ crystal has been performed with the following results: sp. gr. P2₁2₁2₁, Z = 4, a = 5.5360(3) Å, b = 5.8723(6) Å, c = 7.7291(5) Å, and R factors R(F)/wR(F) = 0.86/0.69%. Disordering of iodine site is revealed, which is described in terms of anharmonic atomic displacements. Packing (likely unique) of all structure atoms over two systems of planes rotated by an angle close to the rotation of optical axes (47°) is revealed. The rotation of the plane of polarization of light based on the structural data is calculated for the first time for the α-HIO₃ crystal.     

Crystal structure of the solid solution NH<Subscript>4</Subscript>Al<Subscript>0.62</Subscript>Cr<Subscript>0.38</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 12H<Subscript>2</Subscript>O

The solid solution NH₄Al_0.62Cr_0.38(SO₄)₂ · 12H₂O was studied by X-ray diffraction. The crystal structure was determined in a series of the maximal subgroups Pa3? > R3? > P1? > P1. Reflections forbidden in sp. gr. Pa3? are indicative of symmetry lower than cubic. In the centrosymmetric models under consideration, all sulfate groups are oppositely oriented with respect to each other. In non-centrosymmetric sp. gr. P1, four of the eight sulfate groups have the same orientation, whereas the other four groups are oriented in an opposite direction.     

X-ray diffraction study of Ba<Subscript>3</Subscript>TaFe<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>14</Subscript> single crystal—a promising langasite-type multiferroic

Ba₃TaFe₃Si₂O₁₄ single crystals (sp. gr. P321, Z = 1), promising langasite-type multiferroics, have been grown by floating zone melting. An accurate X-ray diffraction study of Ba₃TaFe₃Si₂O₁₄ single crystal has been performed using two datasets, obtained independently for two different orientations of the same sample on a diffractometer equipped with a CCD area detector at 295 K. Structure refinement is performed based on an averaged dataset: a = 8.5355(1) Å, c = 5.2332(1) Å, sp. gr. P321, Z = 1; the R factors of model structure refinement were found to be R/wR = 1.02/1.23% for 4552 independent reflections. Disordering asymmetry is revealed for the magnetic Fe ion in the 3f site and the Ba cation in the 3e site.     

Accurate structural study of langasite-family Ca<Subscript>3</Subscript>TaGa<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>14</Subscript> crystal

An accurate X-ray diffraction study of Ca₃TaGa₃Si₂O₁₄ single crystal has been performed using two datasets obtained on a diffractometer equipped with a CCD area detector (a = 8.1056(2) Å, c = 4.9800(1) Å, sp. gr. P321, Z = 1, R/wR = 0.486/0.488%). A model structure is determined which is characterized by a high degree of reproducibility of structural parameters. Each site in Ca₃TaGa₃Si₂O₁₄ is occupied by atoms of only one type. Nevertheless, its structural feature is asymmetric disordering of sites of Ca, Ta, Ga, and two out of three oxygen atoms occupying special and general sites. A transition of some part of Ca atoms (~3%) from 3e sites on the twofold symmetry axis to general 6g sites is revealed.     

Nanohematite from Ferruginous Quartzites of Kursk Magnetic Anomaly According to Transmission Electron Microscopy Data

Transmission electron microscopy study of ferruginous quartzite (jaspilites) from the Lebedinsky field of Kursk magnetic anomaly has revealed for the first time hematite nanoformations (about 10 nm in size), sp. gr. R3?, which coexist with hematite, sp. gr. R3?c, in the same crystallographic orientation or manifest themselves as individual nanoinclusions in the substrate of poorly crystallized magnetite. On the assumption that, in correspondence with the energy-dispersive X-ray analysis data, octahedral sites in the hematite structure can be occupied by only Fe cations, several structural models are proposed explain the hematite symmetry lowering to R3?.     

Refined structure of afwillite from the northern Baikal region

The crystal structure of the mineral afwillite [Ca₁₂(H₂O)₈][SiO₄]₄[SiO₂(OH)₂]₄ from the northern Baikal region was refined in a triclinic unit cell with the following parameters: a = 16.330(2) Å, b = 5.6389(6) Å, c = 11.685(1) Å, α = 90.08(1)°, β = 126.446(2)°, γ = 89.95(1)°, and sp. gr. P1. The triclinic unit cell is related to the monoclinic unit cell determined earlier (sp. gr. Cc, a = 16.278(1) Å, b = 5.6321(4) Å, c = 13.236(1) Å, and β = 134.898(3)°) by the transformation matrix [?100/010/101]. The structural model was determined using the phase-correction procedure and refined anisotropically to R = 2.8% based on 3270 independent reflections with F > 3σ(F). The crystal-chemical formula of afwillite was revised. The characteristic features of the IR spectrum of afwillite were explained based on the structural data.     

Crystal structure of low-symmetry rondorfite

The crystal structure of an aluminum-rich variety of the mineral rondorfite with the composition Ca₁₆[Mg₂(Si₇Al)(O₃₁OH)]Cl₄ from the skarns of the Verkhne-Chegemskoe plateau (the Kabardino-Balkarian Republic, the Northern Caucasus Region, Russia) was solved in the triclinic space group with the unit-cell parameters a = 15.100(2) Å, b = 15.110(2) Å, c = 15.092(2) Å, α = 90.06(1)°, β = 90.01(1)°, γ = 89.93(1)°, Z = 4, sp. gr. P1. The structural model consisting of 248 independent atoms was determined by the phase-correction method and refined to R = 3.8% with anisotropic displacement parameters based on all 7156 independent reflections with 7156 F > 3σ(F). The crystal structure is based on pentamers consisting of four Si tetrahedra linked by the central Mg tetrahedron. The structure can formally be refined in the cubic space group (a = 15.105 Å, sp. gr. Fd \(\overline 3 \), seven independent positions) with anisotropic displacement parameters to R = 2.74% based on 579 reflections with F > 3σ(F) without accounting for more than 1000 observed reflections, which are inconsistent with the cubic symmetry of the crystal structure.     

Electrical conductivity of CsCuCl<Subscript>3</Subscript> crystals at structural phase transition

The electrical conductivity σ of CsCuCl₃ single crystals synthesized by the crystallization method from aqueous solutions in the ternary CsCl–CuCl₂–H₂O system has been studied. The σ measurements for CsCuCl₃ crystals have been carried out in the temperature range of 397–455 K, which covers the structural phase transition from the low-temperature (sp. gr. P6₁22, Z = 6) to the high-temperature (sp. gr. P6₃mc, Z = 2) modification at T _tr = 423 ± 8 K. A jump of σ by a factor of ~3 is observed on the σ(T) dependence in the region of the structural transition, which indicates the existence of first-order phase transition. The electric transfer activation enthalpies ΔHσ are found to be 1.0 ± 0.1 eV at T > T _tr and 0.8 ± 0.1 eV at T < T _tr. The σ value for CsCuC_l3 crystals amounts to 7 × 10^–6 S/cm at 455 K.     

Crystalline structure of Cu<Subscript>4</Subscript>SSe

Ternary compound Cu₄SSe has been first synthesized by alloying the Cu, S, and Se elements taken in stoichiometric ratios. An X-ray diffraction study of polycrystalline samples has revealed the synthesized material to be crystallized into the trigonal system with unit-cell parameters а = 4.021(1) Å, с = 6.838(1) Å, and V = 95.75(4) ų; sp. gr. P\(\bar 3\)m1; Z = 1; D_x = 6.333(3) g/cm³. The crystal structure has been solved and refined to the reliability factor R_Bragg = 0.40%.     

Crystal Structure of Two <Emphasis Type="Italic">V</Emphasis>-shaped Ligands with <Emphasis Type="Italic">N</Emphasis>-Heterocycles

Two V-shaped ligands with N-heterocycles, bis(4-(1H-imidazol-1-yl) phenyl)methanone (1), and bis(4-(1H-benzo[d]imidazol-1-yl)phenyl)methanone (2) have been synthesized and characterized by elemental analyses, IR and 1H NMR spectroscopy. Crystal structures of 1 and 2 have been determined by X-ray diffraction. The crystal of 1 is monoclinic, sp. gr. P2₁/c, Z = 4. The crystal of 2 is orthorhombic, sp. gr. Fdd2, Z = 8. X-ray diffraction analyses show that the V-shaped angles of 1 and 2 are 122.72(15)° and 120.7(4)°, respectively. Intermolecular C–H···O, C–H···N, C–H···π, and π···π interactions link the components into three-dimensional networks in the crystal structures.     

Structural study of new compound Bi<Subscript>2.53</Subscript>Li<Subscript>0.29</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> by the powder neutron diffraction method

A new compound of composition Bi_2.53Li_0.29Nb₂O₉ was synthesized in the course of the search for new materials with high ionic conductivity. Its crystal structure was determined from the neutron diffraction data. The new compound Bi_2.53Li_0.29Nb₂O₉ is crystallized in the orthorhombic system, sp. gr. Cmc2₁, and unit-cell parameters a = 24.849(1) Å, b = 5.4536(3) Å, and c = 5.4619(2) Å at T = 290 K (a = 24.843(2) Å, b = 5.4456(5) Å, and c = 5.4546(5) Å at T = 10 K). Within the temperature range 10–870 K, no structural phase transitions were revealed. The atomic coordinates and the thermal factors in the isotropic approximation were refined by the Rietveld method at 290 and 10 K. The data obtained were analyzed based on the calculated local balance of bond strengths.     

Synthesis and Crystal Structure of Dibromido{2-[(4-tert-butylmethylphenyl) iminomethyl]pyridine-κ<Superscript>2</Superscript><Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N'}</Emphasis>Zinc

The title compound [Zn(dip)Br₂] was synthesized using the Schiff base bidentate ligand (E)-4-tert-butyl-N-(pyridine-2-ylmethylene)benzeneamine (dip) and zinc(II) bromide salts. It has been characterized by elemental analysis, X-ray diffraction, and optical spectroscopy. The X-ray diffraction analysis demonstrates that in this structure, the zinc(II) ion is located on an inversion center and exhibits a ZnN₂Br₂ tetrahedral geometry. In this structure the dip ligand is coordinated with zinc(II) ion in a cyclic-bidentate fashion forming a five-membered metallocyclic ring. The compound crystallizes in the monoclinic sp. gr. P2₁/m with a = 9.2700(13) Å, b = 7.6128(11) Å, c = 12.3880(17) Å, and β = 97.021(3)°.     

Crystal structure refinement of Sr<Subscript>3</Subscript>TaGa<Subscript>3</Subscript>Si<Subscript>2</Subscript>O<Subscript>14</Subscript>

An accurate X-ray diffraction study of Sr₃TaGa₃Si₂O₁₄ (STGS) crystal (a = 8.3023(10) Å, c = 5.0853(2) Å, sp. gr. P321, Z = 1, R/wR = 0.59/0.52%, 4004 independent reflections) is performed. The use of two independent data sets obtained on diffractometers with point and 2D detectors made it possible to determine the model structure characterized by the best reproducibility of parameters. The ordered distribution of atoms over crystallographic positions and the anharmonic character of displacements of all cations and one oxygen atom are established.     

Crystal structure of Сu<Subscript>4</Subscript>SeTe

Сu₄SeTe compound has been synthesized. A Сu₄SeTe sample was homogenized by annealing at 750 K for five days. An X-ray diffraction analysis based on powder diffraction data has revealed that the sample crystallizes into the trigonal system with lattice parameters а = 4.178 Å and с = 41.921 Å, sp. gr. \(R\overline 3 m\), Z = 6. Its crystal structure has been determined and refined by the Rietveld method. The final value of the reliability factor R _Bragg is found to be 0.0246.     

Crystal Structure of Liguzinediol, 2,5-Dimethylol-3,6-dimethylpyrazine

The 2,5-dimethylol-3,6-dimethylpyrazine, C₈H₁₂N₂O₂, liguzinediol, has been recently discovered as a potential agent for the treatment of heart failure with low safety risk. The crystal structure of liguzinediol, which has been determined by single-crystal X-ray diffraction analysis, is reported for the first time. The liguzinediol crystal may be obtained from 50% ethanol or ethyl acetate. The compound crystallizes in the monoclinic system with the sp. gr. P2₁/n and the unit cell parameters a = 4.0560(8) Å, b = 12.280(3) Å, c = 8.5370(17) Å, β = 96.93(3)°, Z = 2. The molecule forms S₂-symmetric conformation in the crystal. The hydroxyl H atom forms short intermolecular contacts with the neighbouring pyrazine N atom, which forms the weak hydrogen bonds in the crystal.     

Synthesis,Crystal Structure,and Topology–Symmetry Analysis of a New Modification of NaIn[IO<Subscript>3</Subscript>]<Subscript>4</Subscript>

Crystals of new iodate NaIn[IO₃]₄ were prepared by the hydrothermal synthesis. The unit cell parameters are a = 7.2672(2) Å, b = 15.2572(6) Å, c = 15.0208(6) Å, β = 101.517(3)°, sp. gr. P2₁/c. The formula was determined during the structure determination and refinement of a twinned crystal based on a set of reflections from the atomic planes of the major individual. The refinement with anisotropic displacement parameters was performed for both twin components to the final R factor of 0.050. The In and Na atoms are in octahedral coordination formed by oxygen atoms. The oxygen octahedra are arranged into columns by sharing edges, and the columns are connected by isolated umbrella-like [IO₃]^– groups to form layers. The new structure is most similar to the isoformular iodate NaIn[IO₃]₄, which crystallizes in the same sp. gr. P2₁/c and is structurally similar, but has a twice smaller unit cell and is characterized by another direction of the monoclinic axis. The structural similarity and difference between the two phases were studied by topologysymmetry analysis. The formation of these phases is related to different combinations of identical one-dimensional infinite chains of octahedra.     

X-ray diffraction study of thiocarbamide hydrochloride

Thiocarbamide hydrochloride single crystals forming a salt with the composition [(NH₂)₂CSH]⁺Cl^? are studied by the X-ray diffraction method. The tetragonal crystals have the unit-cell parameters a = 7.556(1) Å and c = 18.329(3) Å, V = 1046.5 ų, Z = 8, ρ_calcd = 1.436 g/cm³, sp. gr. P4₁2₁2, and R = 0.050. Each chloride anion in the crystal forms five hydrogen bonds with thee different cations.