Refinement of the crystal structures of synthetic nickel- and cobalt-bearing tourmalines

The crystal structures of synthetic tourmalines with a unique composition containing 3d elements (Ni, Fe, and Co) have been refined: (Ca_0.12?_0.88)(Al_1.69Ni _0.81 ²⁺ Fe _0.50 ²⁺ )(Al_5.40Fe _0.60 ³⁺ )(Si_5.82Al_0.18O₁₈)(BO₃)₃(OH)_3.25O_0.75 I, a = 15.897(5), c = 7.145(2) Å, V = 1564(1) Å; Na_0.91(Ni _1.20 ²⁺ Cr _0.96 ³⁺ Al_0.63Fe _0.18 ²⁺ Mg_0.03)(Al_4.26Ni _1.20 ²⁺ Cr _0.48 ³⁺ Ti_0.06)(Si_5.82Al_0.18)O₁₈(BO₃)₃(OH)_3.73O_0.27 II, a = 15.945(5), c = 7.208(2) Å, V = 1587(1) ų and Na_0.35(Al_1.80Co _1.20 ²⁺ )(Al_5.28Co _0.66 ²⁺ Ti_0.06)(Si_5.64B_0.36)O₁₈(BO₃)₃(OH)_3.81O_0.19 III, a = 15.753(8), c = 7.053(3) Å, V = 1516(2) ų. The reliability factors are R ₁ = 0.038?0.057 and wR ₂ = 0.041–0.060. It is found that 3d elements occupy both Y- and Z positions in all structures. The excess positive charge is compensated for due to the incorporation of divalent oxygen anions into the O3(V)+O1(W) positions.     

Synthesis and crystal structure of Na<Subscript>3</Subscript>(H<Subscript>3</Subscript>O)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>· H<Subscript>2</Subscript>O

Single crystals of the compound Na₃(H₃O)[UO₂(SeO₃)₂]₂ · H₂O (I) have been synthesized, and their structure has been investigated using X-ray diffraction. Compound I crystallizes in the triclinic system with the unit cell parameters a = 9.543(6)Å, b = 9.602(7)Å, c = 11.742(8)Å, α = 66.693(16)°, β = 84.10(2)°, γ = 63.686(14)°, space group P \(\bar 1\), Z = 2, and R = 0.0734. The uranium-containing structural units of the crystals are [UO₂(SeO₃)₂]^2? chains, which belong to the crystal-chemical group AB ² B ¹¹ (A = UO ₂ ²⁺ , B ² = SeO ₃ ^2? , B ¹¹ = SeO ₃ ^2? ) of the uranyl complexes. The structures of the compounds containing the [UO₂(SeO₃)₂]^2? anionic complexes are compared.     

Synthesis and X-ray diffraction study of new uranyl malonate and oxalate complexes with carbamide

Two new malonate-containing uranyl complexes with carbamide of the formulas [UO₂(C₃H₂O₄)(Urea)₂] (I) and [UO₂(C₃H₂O₄)(Urea)₃] (II), where Urea is carbamide, and one uranyl oxalate complex of the formula [UO₂(C₂O₄)(Urea)₃] (III) were synthesized, and their crystals were studied by X-ray diffraction. The main structural units in crystals I are the electroneutral chains [UO₂(C₃H₂O₄)(Urea)₂]_∞ belonging to the crystal-chemical group AT¹¹M₂¹ (A = UO₂²⁺, T¹¹ = C₃H₂O₄^2-, M¹ = Urea) of uranyl complexes. Crystals II and III are composed of the molecular complexes [UO₂(L)(Urea)₃], where L = C₃H₂O₄^2- or C₂O₄^2-, belonging to the crystal-chemical group AB⁰¹M₃¹ (A = UO₂²⁺, B⁰¹ = C₃H₂O₄^2- or C₂O₄^2-, M¹ = Urea). The characteristic features of the packing of the uranium-containing complexes are discussed in terms of molecular Voronoi–Dirichlet polyhedra. The effect of the Urea: U ratio on the structure of uranium-containing structural units is considered.     

Specific features of the crystal structure and magnetic properties of KTaO<Subscript>3</Subscript> produced by electrolysis of melts

The magnetic susceptibility χ(T) at 4.2 K < T < 293 K; the dependence of the magnetic moment on the magnetic field strength, M(H), at 4.2, 77, and 293 K; and the electrical resistivity ρ(T) at 4.2 K < T < 293 K are studied for samples of perovskite-phase KTaO₃ obtained by both solid-phase synthesis (KTaO ₃ ^s ) and deposition on a cathode during electrolysis of melts (KTaO ₃ ^e ). Yellowish white KTaO ₃ ^s powders are diamagnetic and reveal dielectric properties. Dark polycrystalline KTaO ₃ ^e samples with metallic luster are characterized by the dependence ρ(T) typical of metals and additional paramagnetic contribution to the paramagnetic susceptibility as compared with KTaO ₃ ^e . Changes in the properties of KTaO₃ during electrocrystallization are attributed to partial reduction of tantalum. They are revealed in the structural features of KTaO ₃ ^e (excess of tantalum as compared to the stoichiometric composition of KTaO ₃ ^e , deficiency of the oxygen sublattice, and clearly pronounced anharmonicity of atomic vibrations). A change of the cation-anion-cation interactions, occurring owing to the overlapping of oxygen p orbitals with tantalum t_2g orbitals and the formation of impurity levels near the conduction band, leads to the generation of free carriers, which make a paramagnetic contribution to the magnetic susceptibility.     

Synthesis and an X-ray diffraction study of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>]

The synthesis and X-ray diffraction study of compound Rb₂[(UO₂)₂(C₂O₄)₃], which crystallizes in the monoclinic crystal system, are performed. The unit cell parameters are as follows: a = 7.9996(6) Å, b = 8.8259(8) Å, c = 11.3220(7) Å, β = 105.394(2)°, and V = 770.7(1) ų; space group P2₁/n, Z = 2, and R ₁ = 0.0271. [(UO₂)₂(C₂O₄)₃]^2? layers belonging to the AK _0.5 ⁰² T ¹¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , K ⁰² = C₂O ₄ ^2? , and T ¹¹ = C₂O ₄ ^2? ) are uranium-containing structural units of the crystals. The layers are connected with outer-sphere rubidium cations by electrostatic interactions.     

Structures of Tris(2-hydroxyethyl)ammonium Salts of Succinic Acid

Succinic acid salts-tris(2-hydroxyethyl)ammonium succinate (C₆H₁₆NO₃) ₂ ⁺ C₄H₄O ₄ ^2? (monoclinic crystals, sp. gr. P2₁/c, Z = 4) and tris(2-hydroxyethyl)ammonium hydrogen succinate (C₆H₁₆NO₃)⁺C₄H₅O ₄ ^? (monoclinic crystals, sp. gr. P2₁/c, Z = 4)—were synthesized and structurally characterized. The specific features of the three-dimensional structures of tris(2-hydroxyethyl)ammonium salts of succinic acid are considered. The role of interionic electrostatic interactions in the structure stabilization and the formation of products of composition 1: 1 and 1: 2 derived from succinic acid is discussed.     

Synthesis and structure of (Rb<Subscript>0.50</Subscript>Ba<Subscript>0.25</Subscript>)[UO<Subscript>2</Subscript>(CH<Subscript>3</Subscript>COO)<Subscript>3</Subscript>]

A new compound (Rb_0.50Ba_0.25)[UO₂(CH₃COO)₃] is synthesized and its crystal structure is studied by X-ray diffraction. The compound crystallizes in the form of yellow plates belonging to the cubic crystal system. The unit cell parameter a = 17.0367(1) Å, V = 4944.89(5) ų, space group I \(\bar 4\)3d, Z = 16, and R = 0.0182. The coordination polyhedron of the uranium atom is a hexagonal bipyramid with oxygen atoms of three acetate groups and the uranyl group in the vertices. The crystal chemical formula of the uranium-containing group is AB ₃ ⁰¹ (A = UO ₂ ²⁺ , B ⁰¹ = CH₃COO^?). The oxygen atoms of the acetate groups that enter the coordination polyhedron of uranium are bound to barium and rubidium atoms.     

Synthesis and crystal structure of [UO<Subscript>2</Subscript>CrO<Subscript>4</Subscript>(C<Subscript>5</Subscript>NH<Subscript>5</Subscript>COO)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)]·2H<Subscript>2</Subscript>O

Crystals of UO₂CrO₄(C₅NH₅COO)₂(H₂O)] · 2H₂O are synthesized and their structure is studied by X-ray diffraction. The compound crystallizes in the triclinic crystal system. The unit cell parameters are as follows: a = 7.0834(10) Å, b = 10.6358(14) Å, c = 12.9539(17) Å, α = 75.096(2)°, β = 74.490(2)°, and γ = 80.657(2)°; V = 904.1(2) ų, space group P \(\bar 1\), Z = 2, and R = 0.026. The structure is built of [UO₂CrO₄(C₅NH₅COO)₂(H₂O)]₂ centrosymmetric dimers, which are linked into a framework by a system of hydrogen bonds involving inner-sphere and outer-sphere water molecules. The coordination number of the U(VI) atom is seven, and the coordination polyhedron is a pentagonal bipyramid with the oxygen atoms of the uranyl group, two chromate groups, two molecules of isonicotinic acid, and a water molecule at the vertices. The crystal chemical formula of the [UO₂CrO₄(C₅NH₅COO)₂(H₂O)]₂ dimer is represented as AB ² M ₃ ¹ , where AB ² M ₃ ¹ , where A = UO ₂ ²⁺ , B ² = CrO ₄ ^2? , and M ¹ = = C₅NH₄COOH and H₂O.     

Ionic conductivity of ScF<Subscript>3</Subscript> single crystals (ReO<Subscript>3</Subscript> type)

Electrical conductivity σ of ScF₃ single crystals (sp. gr. \(Pm\overline 3 m\), ReO₃ structure type) has been studied by impedance spectroscopy and compared with the electrical conductivity of rare earth HoF₃ (β-YF₃ type) and LaF₃ (tysonite type) trifluorides. ScF₃ crystals obtained by Bridgman directional solidification have ionic conductivity σ = 4 × 10^–8 S/cm at 673 K. It is smaller than the σ values for LaF₃ (sp. gr. \(P\overline 3 c1\)) and HoF₃ (sp. gr. Pnma) single crystals by a factor of 10⁴–10⁵. The low conductivity of ScF₃ crystals is due to the weak coordinating ability (coordination number CN = 6) and low electronic polarizability (α_cat = 1.1 ų) of Sc³⁺ ions. Mobile V_F⁺ vacancies and less mobile interstitial V_i^- ions (defects are formed according to the Frenkel mechanism) are involved in the ion transport. HoF₃ and LaF₃ single crystals have a high coordinating ability (CN = 9 for Ho³⁺ and CN = 11 for La³⁺) and a high electronic polarizability of cations (α_cat = 1.6–1.9 ų for Ho³⁺ and α_cat = 2.2 ų for La³⁺). Only mobile V_F⁺ vacancies (defects are formed according to the Schottky mechanism) are involved in ion transport.     

Crystal structure of complex natural aluminum magnesium calcium iron oxide

The structure of a new natural oxide found near the Tashelga River (Eastern Siberia) was studied by X-ray diffraction. The pseudo-orthorhombic unit cell parameters are a = 5.6973(1) Å, b = 17.1823(4) Å, c = 23.5718(5) Å, β = 90°, sp. gr. Pc. The structure was refined to R = 0.0516 based on 4773 reflections with |F| > 7σ(F) taking into account the twin plane perpendicular to the z axis (the twin components are 0.47 and 0.53). The crystal-chemical formula (Z = 4) is Ca₂Mg ₂ ^IV Fe ₂ ^(2+)IV [Al ₁₄ ^VI O₃₁(OH)][Al ₂ ^IV O][Al^IV]AL^IV(OH)], where the Roman numerals designate the coordination of the atoms. The structure of the mineral is based on wide ribbons of edge-sharing Al octahedra (an integral part of the spinel layer). The ribbons run along the shortest x axis and are inclined to the y and z axes. The adjacent ribbons are shifted with respect to each other along the y axis, resulting in the formation of step-like layers in which the two-ribbon thickness alternates with the three-ribbon thickness. Additional Al octahedra and Mg and Fe²⁺ tetrahedra are located between the ribbons. The layers are linked together to form a three-dimensional framework by Al tetrahedra, Ca polyhedra, and hydrogen bonds with the participation of OH groups.     

X-ray diffraction study of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(CrO<Subscript>4</Subscript>)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 4H<Subscript>2</Subscript>O

The compound Rb₂[(UO₂)₂(CrO₄)₃(H₂O)₂] · 4H₂O was studied by X-ray diffraction. The crystals are monoclinic, a = 10.695(2) Å, b = 14.684(3) Å, c = 14.125(3) Å, β = 108.396(4)°, sp. gr. P2₁/c, Z = 4, V = 2104.9(7) ų, and R = 0.0491. The main structural units are layers consisting of [(UO₂)₂(CrO₄)₃(H₂O)₂]^2? anions belonging to the crystal-chemical group A ₂ T ₂ ³ B ²M ₂ ¹ (A = UL ₂ ²⁺ , T ³ and B ² are CrO ₄ ^2? , and M ¹ is H₂O) of uranyl complexes. The uranium-containing layered groups are held together by electrostatic interactions with rubidium cations, as well as by hydrogen bonds with the participation of inner- and outer-sphere water molecules.     

Thermal Expansion of EuF<Subscript>2 + <Emphasis Type="Italic">x</Emphasis></Subscript> Single Crystals and Their Thermal Stability

Thermal expansion of an EuF_2.136 nonstoichiometric crystal with the fluorite structure type (Eu _0.864 ²⁺ Eu _0.136 ³⁺ F_2.136, lattice parameter 5.82171(5) Å) has been experimentally investigated in the temperature range of 9–500 K. The coefficient of thermal expansion is α = 15.8 × 10^–6 K^–1 at T = 300 K. The observed anomalies in the behavior of the coefficient of thermal expansion at T > 400 K are related to the oxidation processes with partition of Eu²⁺ ions. It is established by differential scanning calorimetry that the onset temperature of EuF_{2 + x} oxidation in air is 430 K and that this process occurs in three stages. X-ray diffraction analysis shows that the oxidation is accompanied by the formation of a phase mixture based on two modifications of the Eu _{1– y} ³⁺ Eu _y ²⁺ F_3–y solid solution with the structure types of tysonite (LaF₃), orthorhombic β-YF₃ phase, and europium oxyfluorides of variable composition EuO_1–xF_{1 + 2x}, with dominance of the latter.     

Investigation of structural transformations in pyridine nitrate at low temperatures and high pressures

The structural transformations in pyridine nitrate PyHNO₃ (C₅D₅NHNO₃) are investigated by neutron diffraction in the temperature range 16–300 K at normal pressure and in the high-pressure range 0–3.5 GPa at room temperature. A new high-pressure phase with a monoclinic structure (space group P2₁/c) is revealed in the PyHNO₃ compound at pressures P > P_tr ～ 1 GPa. The geometry of hydrogen bonds and the coordination of the PyH⁺ and NO ₃ ^? ions in the structure of the PyHNO₃ compound are studied as a function of the temperature and pressure.     

Structure and some properties of [UO<Subscript>2</Subscript>(C<Subscript>5</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>O)<Subscript>5</Subscript>](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

Compound [UO₂(C₅H₁₂N₂O)₅](ClO₄)₂ is synthesized and characterized by thermogravimetry, IR spectroscopy, and X-ray diffraction. The compound crystallizes in the monoclinic crystal system; a = 15.2985(9) Å, b = 26.9676(15) Å, c = 20.6962(11) Å, β = 100.697(1)°, space group P2₁/c, Z = 8, and R = 0.0445. Discrete [UO₂(C₅H₁₂N₂O)₅]²⁺ groups belonging to the AM ₅ ¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ and M ¹=C₅H₁₂N₂O) are uranium-containing structural units of the crystals.     

Synthesis and crystal chemical characteristics of the structure of <Emphasis Type="Italic">M</Emphasis><Subscript>0.5</Subscript>Zr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> phosphates

Double phosphates of zirconium and metals with an oxidation degree of +2 of the composition M_0.5Zr₂(PO₄)₃ (M = Mg, Ca, Mn, Co, Ni, Cu, Zn, Sr, Cd, and Ba) are synthesized and characterized by X-ray diffraction methods and IR spectroscopy. The crystal structures of all the compounds are based on three-dimensional frameworks of corner-sharing PO₄-tetrahedra and ZrO₆-octahedra. Phosphates with large Cd²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ cations octahedrally coordinated with oxygen atoms form rhombohedral structures (space group R3), whereas phosphates with small tetrahedrally coordinated Mg²⁺, Ni²⁺, Cu²⁺, Co²⁺, Zn ²⁺, and Mn²⁺-cations are monoclinic (space group P2₁/n). The effect of various structure-forming factors on the M_0.5Zr₂(PO₄)₃ compounds with a common structural motif but different symmetries are discussed.     

Complete normalizer for a direct product of three-dimensional rotation groups

A normalizer of the symmetry group defined on a three-dimensional sphere S ³ of rotation is considered in the four-dimensional Euclidean space E ⁴. The sphere S ³ is treated as the first approximation of the three-dimensional crystallographic space. The analysis of the normalizer N of the direct product G = G ₁ × G ₂ of space crystallographic rotation groups G ₁ and G ₂ is reduced to the study of transformations characterized by the positive determinants of the subgroups N ⁺ (G ₁ and N ⁺(G ₂). These subgroups correspond to the Euclidean normalizers N = N ⁺ (G ₁) × N ⁺(G ₂) of the components of the direct product. We derived a table including the groups of automorphisms induced by the transformations corresponding to the normalizers under study. Analyzing the general operation of multiplication of three-dimensional rotations in E ⁴, we refined the distribution of the supersymmetry operators of the three-dimensional sphere of rotations, S ³, for the symmetry groups considered earlier.     

Synthesis and structure of iridium complex with thiocarbamide

A single crystal of the [Ir(Thio)₂Cl₄][Ir(Thio)₄Cl₂] compound synthesized by the reaction of K₃[IrCl₆] with thiocarbamide (Thio, SC(NH₂)₂) in a microwave field is investigated using X-ray diffraction. The compound crystallizes in the monoclinic crystal system with space group Cc(C _s ⁴ ). The unit cell parameters are as follows: a = 13.554(1) Å, b = 8.251(1) Å, c = 24.992(2) Å, β = 92.58(1)°, V = 2791.87(10) ų, and Z = 4. The compound has an island structure with two crystallographically independent iridium atoms. Thiocarbamide is coordinated to the central atom through the sulfur atom. The coordination sphere of the Ir(1) atom involves two Cl atoms and four S atoms, whereas the coordination sphere of the Ir(2) atom consists of four Cl atoms and two S atoms. The assignment of the bands in the IR absorption spectrum of the synthesized compound is presented. The thermal behavior of the compound in air is investigated.     

Synthesis and crystal structure of the iridium(I) carbene complex with a pair of hydrogen wing tips

The iridium(I) cyclooctadiene complex with two (3-tert-butylimidazol-2-ylidene) ligands [(H-Im^tBu)₂Ir(COD)]⁺PF₆^? (C₂₂H₃₂PF₆IrN₄) has been prepared, and its crystal structure is determined by X-ray diffraction. Complex exhibits slightly distorted square planar configurations around the metal atom, which is coordinated by two H-Im^tBu ligands and one cyclooctadiene group. The new iridium carbene complex has a pair of hydrogen wing tips. The Ir?C_carbene bond lengths are 2.066(5) and 2.052(5) Å, and the bond angle C?Ir?C between these bonds is 95.54(19)°. The dihedral angle between two imidazol-2-ylidene rings is 86.42°.     

Synthesis,conductivity, and the crystal structure of a new stable metal, β″-(<Emphasis Type="Italic">DOEO</Emphasis>)<Subscript>2</Subscript>HSeO<Subscript>4</Subscript> · H<Subscript>2</Subscript>O

The stable metal β″-(DOEO)₂HSeO₄ · H₂O I) based on a new donor compound, 3,4-(1,4-dioxanediyl-2,3-dithio)-3′,4′-ethylenedioxo-2,5,2′,5′-tetrathiafulvalene] (DOEO), is synthesized and structurally characterized for the first time. The synthesis is performed by the electrocrystallization technique (direct current density j = 2 × 10^?6 A/cm²). The crystals are triclinic, and the unit cell parameters are as follows: a = 5.495(1) Å, b = 9.715(2) Å, c = 16.878(3) Å, α = 83.52(3)°, β = 82.54(3)°, γ = 73.51(3)°, Z = 1, and space group \(P\bar 1\). The salt has a layered structure. The DOEO^1/2+ radical cation layers are aligned parallel to the ab planes. The HS_eO ₄ ^? · H₂O solvated anions are located in channels along the a axis and are disordered over two positions near the center of symmetry (1/2 0 0) with a probability of 50%. The conductivity of the salt is equal to 300–400 Ω^?1 cm^?1 at room temperature and increases upon cooling to the boiling point of liquid helium (4.2 K) by a factor of 100–200 depending on the sample.