The crystal and molecular structure of a bismonothioacetylacetonate complex of copper, Cu(CH3CSCHCOCH3)2: An analysis of cis vs. trans isomerism

The crystal and molecular structure of cis-Cu(CH₃CSCHCOCH₃)₂ has been determined by X-ray diffraction. The complex crystallizes in the triclinic space group P with lattice parameters a = 10.588(2) Å, b = 11.445(2) Å, c = 11.779(2) Å, = 88.13(1)°, = 63.73(2)°, = 86.57(2)°, V = 1277.6(4) ų, Z = 4. The asymmetric unit consists of two crystallographically independent molecules. The approximate cis square planar geometry of thecomplex is consistent with the relatively large dipole moment observed in solution. Density functional calculations predict that a pseudo-tetrahedral conformation of the molecule would be on the order of 40 kJ mol^–1 higher in energy than the crystallographicallydetermined conformation, while a trans conformation would have approximately the same energy. This suggests that the cis conformer observed in the solidstate coexists in equilibrium with the trans conformer in solution.     

Synthesis and crystal structure of anhydrous copper suberate: [Cu<Subscript>2</Subscript>(OOC-(CH<Subscript>2</Subscript>)<Subscript>6</Subscript> -COO)<Subscript>2</Subscript>]

The title compound [Cu₂(OOC-(CH₂)₆-COO)₂] was synthesized and its crystal structure has been determined by single crystal X-ray diffraction methods. The complex crystallizes in the triclinic space group P-1 with a=5.1077(5) ?, b=8.362(2) ?, c=11.378(2) ?, α=93.773(6)°, β=97.587(9)°, γ=90.493(’9)° and D _cal=1.629 mg/m³ for Z=1.  The structure is polymeric and consists of discrete anhydrous centrosymmetric binuclear units [Cu₂(OOC-(CH₂)₆-COO)₂]. The two copper(II) centres bridged by the suberate groups in a syn-syn conformation, are in pentacoordinated distorted square-pyramidal coordination environment, with an intramolecular Cu–Cu distance of 2.5793(10) ?. Each binuclear unit, related to the next through μ_oxo bridges with a Cuμ_oxo–Cuμ_oxo separation of 3.2326(10)?, defines infinite chains of one-edge sharing CuO₅ square pyramid.     

The behavior of thermal conductivity in the chaotic phase of [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystal

A thermal investigation of the modulated structure dynamics at the transition between metastable states in the incommensurate phase of [N(CH₃)₄]₂ZnCl₄ crystal have been performed. It is established that the anomalous behavior of the thermal conductivity in the absence of a defect-density wave is due to the inelastic scattering of thermal phonons from critical phonons of the soft optical branch. In the presence of a defect-density wave, the anomalous increase in thermal conductivity is caused by the existence of a chaotic phase and is related to the contribution that soft optical phonons make to the heat transfer due to the increase in their group velocity.     

Growth and crystal structure of binary molybdate CsFe(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>

CsFe(MoO₄)₂ single crystals have been grown by solution-melt crystallization with a charge-to-solvent ratio of 1: 3 (with Cs₂Mo₃O₁₀ used as a solvent). The crystal structure of this compound has been refined by X-ray diffraction (X8 APEX automatic diffractometer, MoK _α radiation, 356 F(hkl), R = 0.0178). The trigonal unit cell has the following parameters: a = b = 5.6051(2) Å, c = 8.0118(4) Å, V = 217.985(15) ų, Z = 1, ρ_calc = 3.875 g/cm³, and sp. gr. P \(\bar 3\) m1. The structure is composed of alternating layers of FeO₆ octahedra (with MoO₄ tetrahedra attached by sharing vertices) and CsO₁₂ icosahedra.     

Crystal structure of Rb<Subscript>2</Subscript>[Ti(VO<Subscript>2</Subscript>)<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>]

The crystal structure of the new compound Rb₂[Ti(VO₂)₃(PO₄)₃] obtained by hydrothermal synthesis in the RbCl-TiPO₄-V₂O₅-B₂O₃-H₂O system (a = 13.604(2) Å, c = 9.386(2) Å, sp. gr. P6cc, Z = 4, ρ_calcd = 3.32 g/cm³) has been studied by X-ray diffraction (Xcalibur-S-CCD diffractometer, R = 0.038). It is shown that the isotypism of Rb₂[Ti(VO₂)₃(PO₄)₃] and Cs₂[Ti(VO₂)₃(PO₄)₃] is caused by the flexibility of a mixed anionic framework composed of phosphorus tetrahedra, vanadium five-vertex polyhedra, and titanium octahedra (bases of the crystal structures of these compounds). The topological correlations between the structures of titanium-vanadyl phosphates and benitoite and beryl silicates are analyzed.     

Refinement of the crystal structure of rhombohedral KU<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> as a representative of orthophosphates with the NaZr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> structure

The crystal structure of the high-temperature β modification of synthetic orthophosphate KU₂(PO₄)₃ was refined from powder X-ray diffraction data by the Rietveld method: sp. gr. \(R\bar 3c\), the unit-cell parameters a= 9.113(1) Å and c= 24.997(1) Å. The isotropic refinement converged to R _wp = 6.15, R _B = 2.14, R _F = 3.52, and S = 0.42. It was confirmed that β-KU₂(PO₄)₃ belongs to the structure type of sodium zirconium phosphate containing an actinide atom in a sixfold (octahedral) coordination formed by oxygen atoms, which is unusual for orthophosphates. The principal interatomic distances and bond angles in the structure are reported.     

The domain structure of Cs<Subscript>3</Subscript>H(SeO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals

The characteristics of the changes in the domain structure of Cs₃H(SeO₄)₂ crystals have been studied in a wide temperature range. An anomalous change in the domain structure in the temperature range near the superprotonic phase transition was found. The anomalies in this temperature range were also found by differential scanning calorimetry. The characteristics of the changes in the domain structure in different phases are compared.     

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.     

Crystal and Molecular Structure of Dichloro(ethylenediamine)gold(III) Nitrate: [Au(NH<Subscript>2</Subscript>CH<Subscript>2</Subscript>CH<Subscript>2</Subscript>NH<Subscript>2</Subscript>)Cl<Subscript>2</Subscript>]NO<Subscript>3</Subscript>

Abstract  The gold(III) atom in [Au(NH₂CH₂CH₂NH₂)Cl₂]NO₃ is chelated by the ethylenediamine (en) ligand and the approximately square planar geometry is completed by two chloride atoms. Weak Au···O and Au···Cl contacts are noted above and below the square plane leading to a tetragonally distorted octahedron for the gold(III) center. Extensive charge-assisted hydrogen bonding of the type N–H···O leads to the formation of a 2-D array and layers are consolidated into a 3-D network via C–H···O and C–H···Cl contacts. The compound crystallizes in the orthorhombic space group Pbca with a = 10.3380(11) ?, b = 8.2105(7) ?, c = 19.625(2) ?, and Z = 8. Index Abstract  Square planar complex cations form additional Au···O and Au···Cl interactions to form a tetragonally distorted octahedron for gold. The ionic components are connected into a 2-D array via charge-assisted N–H···O hydrogen bonding interactions.      

Low-temperature X-ray diffraction studies of [(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>NH<Subscript>2</Subscript>]<Subscript>5</Subscript>Cd<Subscript>3</Subscript>Cl<Subscript>11</Subscript> crystals

[(CH₃)₂NH₂]₅Cd₃Cl₁₁ crystals are grown by the method of isothermal evaporation from saturated aqueous solutions containing dimethylamine and cadmium chlorides, [(CH₃)2NH₂]Cl and CdCl_2.5H₂O. The crystal grown are studied by the X-ray diffraction method. It is established that the crystals are orthorhombic with the unit-cell parameters at room temperature a = 18.115 ± 0.004 Å, b = 11.432 ± 0.002 Å, and c = 15.821 ± 0.003 Å. The unit-cell parameters a, b, and c of the [(CH₃)₂NH₂]₅Cd₃Cl₁₁ crystals are measured as functions of temperature in the temperature range 100–320 K. The data obtained were used to determine the thermal expansion coefficients along the main crystallographic axes. The temperature curves of the unit-cell parameters and thermal expansion coefficients showed pronounced anomalies in the vicinity of the temperatures T ₁ = 120, T ₂ = 150, and T ₃ = 180 K corresponding to the phase transitions in the [(CH₃)₂NH₂]₅Cd₃Cl₁₁ crystals. The crystals are also characterized by a pronounced anisotropy of thermal expansion.     

Synthesis and structure of new thorium phosphate CaGdTh(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Phosphate CaGdTh(PO₄)₃ was prepared by thermal treatment of a mixture of oxides. The final temperature was 1400°C. The phosphate was characterized by powder X-ray diffraction analysis and IR spectroscopy. The crystal structure was studied by the Rietveld method. The compound crystallizes in the monazite structure type (sp. gr. P2₁/n). A comparative analysis of the structures of this phosphate and cerium orthophosphate CePO₄ was carried out.     

New isoformula iodates In(IO<Subscript>3</Subscript>)<Subscript>3</Subscript> and Sm(IO<Subscript>3</Subscript>)<Subscript>3</Subscript> with different crystal structures: Specific structural features of I<Superscript>5+</Superscript> compounds

New iodates, namely, In(IO₃)₃ (space group R \(\bar 3\)) and Sm(IO₃)₃ (space group P2₁/a), are synthesized under hydrothermal conditions. The original crystal structure of the In(IO₃)₃ compound is determined without prior knowledge of the chemical formula. The Sm(IO₃)₃ compound is isostructural to the Gd(IO₃)₃ compound. The [IO₄]^3- tetrahedra with three short I-O bonds have an umbrella coordination, which is characteristic of pentavalent iodine, and form anionic radicals, such as a ring radical in the In(IO₃)₃ iodate, a triple helix in the isoformula compound Fe(IO₃)₃, a complex chain in the Sm(IO₃)₃ iodate, and a linear triortho group in the Sm(IO₃)₃·H₂O compound. All radicals contain triortho groups. The structural differences are determined by different ionic radii and shapes of the coordination polyhedra of the cations (indium and iron octahedra and an eight-vertex samarium polyhedron).     

Dilatometric and ultrasound study of [NH<Subscript>2</Subscript>(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>]MnCl<Subscript>3</Subscript> · 2H<Subscript>2</Subscript>O crystals

The unit-cell parameters of [NH₂(CH₃)₂]MnCl₃ · 2H₂O crystals are determined by X-ray diffraction analysis and the velocities of longitudinal ultrasonic waves in these crystals are measured by the echo-pulse method in the temperature range 100–315 K. The coefficients of thermal expansion along the principal crystallographic axes are derived from the temperature dependences of the unit-cell parameters. The temperature dependences of the characteristics studied reveal kink anomalies at temperatures of ～125, 179, 203, 260, and 303 K. These anomalies are indicative of structural transformations in the [NH₂(CH₃)₂]MnCl₃ · 2H₂O crystals, which may be related to the dynamics of dimethylammonium cations.     

Crystal structure of (Al,V)<Subscript>4</Subscript>(P<Subscript>4</Subscript>O<Subscript>12</Subscript>)<Subscript>3</Subscript>, archetype of double cubic ring tetraphosphate

The crystal structure of the (Al,V)₄(P₄O₁₂)₃ solid solution, obtained in the single-crystal form by hydrothermal synthesis in the Al(OH)₃-VO₂-NaCl-H₃PO₄-H₂O system, has been solved by X-ray diffraction analysis (Xcalibur-S-CCD diffractometer, R = 0.0257): a = 13.7477(2) Å, sp. gr. I \(\bar 4\)3d, Z = 4, and ρ_calcd = 2.736 g/cm³. It is shown that the crystal structure of the parent cubic Al₄(P₄O₁₂)₃ modification can formally be considered an archetype for the formation of double isosymmetric tetraphosphates on its basis.     

Synthesis and structural study of Rb<Subscript>2</Subscript>FeZr(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> phosphate with langbeinite structure

A new orthophosphate of rubidium, iron, and zirconium, crystallizing in the langbeinite structure (cubic system, sp. gr. P2₁3, Z = 4), was synthesized and investigated by X-ray powder diffraction and IR spectroscopy. The structure of the Rb₂FeZr(PO₄)₃ phosphate was refined by the Rietveld method using the neutron powder diffraction data (DN-2 time-of-flight diffractometer; Joint Institute for Nuclear Research, Dubna). This structure is characterized by a mixed framework [FeZr(PO₄)₃] with Rb atoms located in large cavities. Fe³⁺ and Zr⁴⁺ cations are distributed statistically over two independent crystallographic positions.     

Synthesis and crystal structure of Pb<Subscript>3</Subscript>[IO<Subscript>3</Subscript>]<Subscript>2</Subscript>Cl<Subscript>4</Subscript>, a representative of a new iodate-chloride class of compounds

Compound Pb₃[IO₃]₂Cl₄ (space group C12/c1), representing a new iodate-chloride class of compounds, is synthesized under hydrothermal conditions. Only two minerals, schwartzembergite Pb₃[IO₃]Cl₂O(OH) and seeligerite Pb₃[IO₃]Cl₃O, the structures of which are unknown, are close in composition to this compound. In the iodate-chloride studied, the pentavalent iodine atom has an umbrella-like coordination, which is typical of iodates and consists of three O atoms at short distances and the fourth O atom at a longer distance. [IO₄]³⁻ tetrahedra share edges to form pairs. Lead ions form layers parallel to the ab plane. Along the c axis, these layers alternate with layers of iodate groups. Pb atoms are coordinated by O atoms of iodate groups and Cl atoms. The coordination sphere of the Pb(1) atom contains a free sector which is directed to more distant halogen atoms and possibly accommodates the lone electron pair.     

Ionic conductivity of KMgCr(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> molybdate

The ionic conductivity σ of KMgCr(MoO₄)₃ crystal has been investigated in a temperature range of 575–932 K by impedance spectroscopy in the frequency range of (5–5) × 10⁵ Hz. Ternary molybdate was obtained from the initial MgMoO₄ and KCr(MoO₄)₂ reagents by solid-phase technique in air at 923–973 K for 200 h. The temperature dependence σ(T) of a ceramic sample exhibits a jump of σ by a factor of about 4 at 833 ± 5 K, which is caused by the first-order phase transition. The σ value above the phase-transition temperature reaches 6 × 10^–4 S/cm (932 K) at an ion-transport activation enthalpy of 0.84 ± 0.05 eV. The most likely carriers in KMgCr(MoO₄)₃ are K⁺ cations.     

Molecular structure of [(C<Subscript>5</Subscript>H<Subscript>5</Subscript>)<Subscript>2</Subscript>(C<Subscript>5</Subscript>H<Subscript>4</Subscript>CH<Subscript>3</Subscript>)(C<Subscript>4</Subscript>H<Subscript>8</Subscript>O)Sm]

The mixed tris-cyclopentadienyl tetrahydrofuranato samarium complex bis-(cyclopentadienyl) methylcyclopentadienyl tetrahydrofuranato samarium (I) was synthesized by reaction of (C₅H₅)₂SmCl with methyl cyclopentadienyl sodium in THF. [(C₅H₅)₂(C₅H₄CH₃)(C₄H₈O)Sm] (I) was characterized by elemental analyses—IR spectra and MS spectra. The structure of [(C₅H₅)₂(C₅H₄CH₃)(C₄H₈O)Sm] (I), which has two slightly different independent molecules per asymmetric unit, has been elucidated through complete X-ray analysis. The crystals are monoclinic, with a = 12.791(3) Å, b = 10.467(2) Å, c = 26.108(5) Å, β = 98.22(2)°, and space group Cc, R = 0.0381 for 2103 observed-reflection with I ≥ 3σ(I).     

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.     

The Influence of Cation Substitution on the Kinetics of Phase Transitions in Crystals of (K,NH<Subscript>4</Subscript>)<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> Solid Solutions

The structure of (K_0.967(NH₄)_0.033)₃H(SO₄)₂ crystals, belonging to the K₃H(SO₄)₂–(NH₄)₃H(SO₄)₂–H₂O salt system, has been investigated by X-ray structural analysis. The room-temperature characteristics of the atomic structure of these crystals are found to be as follows: sp. gr. C2/c, Z = 4, a = 14.7025(4) Å, b = 5.6859(2) Å, c = 9.7885(3) Å, and R/wR = 0.021/0.030%. The thermal and optical properties of (K,NH₄)₃H(SO₄)₂ and K₃H(SO₄)₂ single crystals have been investigated and compared in a temperature range of 295–500 K.