Crystal structure of [(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>P][Ni(B<Subscript>9</Subscript>C<Subscript>2</Subscript>H<Subscript>11</Subscript>)<Subscript>2</Subscript>]·CCl<Subscript>4</Subscript>

A new compound containing the tetraphenylphosphonium cation and the nickel(III) bisdicarbollyl anion, [(C₆H₅)₄P][Ni(B₉C₂H₁₁)₂]·CCl₄, was synthesized and investigated by XRD at room temperature (295 K). Crystal data: C₂₉H₄₂B₁₈PCl₄Ni, M = 816.69, monoclinic, space group P2/c; unit cell parameters a = 13.5873(6) Å, b = 7.1475(2) Å, c = 20.7829(8) Å, β = 94.4595(13)°, V = 2012.2(2) ų, Z = 2, d _calc = 1.348 g/cm³. The structure was solved by direct and Fourier methods and refined by the full-matrix least squares method in an anisotropic (isotropic for H) approximation to the final R ₁ = 0.0466 for 3055 I _hkl ≥ 2σ _I of 23,655 reflections collected and 5618 independent I _hkl (Bruker X8 APEX diffractometer, λMoK _α).     

Transformations of CO<Subscript>2</Subscript> in Two-Phase Systems C<Subscript>8</Subscript>F<Subscript>18</Subscript>–H<Subscript>2</Subscript>O and C<Subscript>6</Subscript>F<Subscript>6</Subscript>–H<Subscript>2</Subscript>O

The transformation of carbon dioxide in aqueous emulsions of perfluorons in the presence of oxygen in the air results in the formation of a mixture of oxalic acid and a minor set of organic compounds C₄–C₈. The maximum CO₂ consumption occurs in the emulsion with the C₈F₁₈: H₂O vol/vol ratio of 1: 0.42 at pH 2.4; the H₂C₂O₄ yield is 11 mol %.     

Crystal structure of Ba<Subscript>3</Subscript>[UO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(NCS)]<Subscript>2</Subscript> · 9H<Subscript>2</Subscript>O

Single crystals of Ba₃[UO₂(C₂O₄)₂(NCS)]₂ · 9H₂O are synthesized and studied by X-ray diffraction. The crystals are orthorhombic, space group Fddd, Z = 16, and the unit cell parameters are a = 16.253(3) Å, b = 22.245(3) Å, c = 39.031(6) Å. The main crystal structural units are mononuclear complex groups [UO₂(C₂O₄)₂NCS]^3? of the crystal-chemical family (AB ₂ ⁰¹ M¹ (A = UO ₂ ²⁺ , B⁰¹ = C₂O ₄ ^2? , M¹ = NCS^?) of the uranyl complexes linked into a three-dimensional framework by electrostatic interactions and hydrogen bonds involving oxalate ions and water molecules.     

Crystal structure of Cs[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)] · H<Subscript>2</Subscript>O

Single crystals of Cs[(UO₂)₂(C₂O₄)₂(OH)] · H₂O were synthesized and structurally studied using X-ray diffraction. The compound crystallizes in monoclinic space group P2₁/m, Z = 2, with the unit cell parameters a = 5.5032(4) Å, b = 13.5577(8) Å, c = 9.5859(8) Å, β = 97.012(3)°, V = 709.86(9) ų, R = 0.0444. The main building units of crystals are [(UO₂)₂(C₂O₄)₂(OH)]^? layers of the A₂K ₂ ⁰² M² (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , and M² = OH^?) crystal-chemical family. Uranium-containing layers are linked into a three-dimensional framework via electrostatic interactions with outer-sphere cations and hydrogen bonds with water molecules.     

Effect of pressure on the oxidative cracking of C<Subscript>2</Subscript>—C<Subscript>4</Subscript> alkanes

The influence of pressure on the oxidative cracking of light alkanes C₂—C₄ was investigated. An elevated pressure reduces the temperature of oxycracking of light alkanes but with further increase in pressure the effect is reduced. The applied pressure decreases the temperature of the total conversion of oxygen while the maximum conversion of alkanes is not influenced. The pressure above atmospheric promotes oxidative cracking reactions but weakly affects thermal processes. At deep conversion of light alkanes, the selectivity towards main products is nearly invariable at the utilized pressures.     

Crystal structure of glycine phosphite C<Subscript>2</Subscript>H<Subscript>5</Subscript>NO<Subscript>2</Subscript>·H<Subscript>3</Subscript>PO<Subscript>3</Subscript>

Single crystal X-ray diffraction study of glycine phosphite C₂H₅NO₂·H₃PO₃ was performed (monoclinic, space group P2₁/c, a = 7.401(3) Å, b = 8.465(3) Å, c = 9.737(3) Å; β = 100.73(5)°, Z = 4). It has been found that one of hydrogen atoms is located at the centre of symmetry forming two strong hydrogen bonds to yield H₄P₂O ₆ ^?2 dimers, while another hydrogen atom is statistically disordered over two positions and organizes the dimers into an infinite corrugated chain. The ordering of this hydrogen atom position and/or displacement of the other one from the centre of symmetry will lead to the loss of symmetry centre and lowering of the point group symmetry from C_2h to piezo-active group C₂ or C _s .     

Crystal structure of Na<Subscript>4</Subscript>[Na<Subscript>2</Subscript>Cr<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>6</Subscript>] · 10H<Subscript>2</Subscript>O

Single crystals of the Na₄[Na₂Cr₂(C₂O₄)₆] · 10H₂O complex were synthesized for the first time. The structure of the complex was determined by X-ray diffraction analysis. The compound crystallizes in the monoclinic crystal system with the unit cell parameters a = 17.290(4) Å, b = 12.521(3) Å, c = 15.149(3) Å, β = 100.45(3)°, Z = 4, space group Cc. Anionic layers [NaCr(C₂O₄)₃] _2n ^4n? can be distinguished in the crystal structure of the complex. The Na⁺ cations and water molecules, involved in the formation of a hydrogen bond network, are located between the anionic layers.     

<Superscript>35</Superscript>Cl NQR for the SbCl<Subscript>3</Subscript> complex with aniline,SbCl<Subscript>3</Subscript>·NH<Subscript>2</Subscript>C<Subscript>6</Subscript>H<Subscript>5</Subscript>

The temperature dependence of the ³⁵Cl NQR frequencies and spin-lattice relaxation times has been investigated for a trigonal-bipyramidal vn complex SbCl₃·NH₂C₆H₅. Thermally activated motion of chlorine atoms (pseudorotation) was not revealed in the complex, in contrast to the vπ complexes of SbCl₃ with related molecular structures. The high potential barrier of pseudorotation in the aniline complex is likely to be due to the unusually high nonequivalence of Sb-Cl chemical bonds.     

Thermodynamic analysis of the structure of aqueous solutions of C<Subscript>12</Subscript>–C<Subscript>18</Subscript> hydrocarbons

Thermodynamic cycles including the increments \(\Delta G_{CH_2 }^0 , \Delta H_{CH_2 }^0 \), and \(T\Delta S_{CH_2 }^0 \) were constructed for dissolution, evaporation, hydrophobic hydration of C₅–C₉ hydrocarbons, and transfer from vapor (\(\Delta G_{CH_2 }^0 \) = ?0.7 kJ·mol^?1, \(\Delta H_{CH_2 }^0 \) = 2.9 kJ·mol^?1, \(T\Delta S_{CH_2 }^0 \) = 3.6 kJ·mol^?1) and water (\(\Delta G_{CH_2 }^0 \) = ?1.4 kJ·mol^?1, \(\Delta H_{CH_2 }^0 \) = 5.8 kJ·mol^?1, \(T\Delta S_{CH_2 }^0 \) = 7.2 kJ·mol^?1) to micelles of C₁₂–C₁₈ hydrocarbons. The formation of bistable hydrated micelles of C₁₂–C₁₈ is explained by a transition between the order-disorder states in an assembly of small (nano) systems of water. The extensive parameters of small systems and critical phenomena predicted by fluctuation theory are discussed.     

Ion transport studies in nanocomposite polymer electrolyte membrane of PVA–[C<Subscript>4</Subscript>C<Subscript>1</Subscript>Im][HSO<Subscript>4</Subscript>]–SiO<Subscript>2</Subscript>

The paper reports the effect of SiO₂ nano-filler on structural, thermal, and ion transport properties of polymer electrolyte system comprising polyvinyl alcohol (PVA) and 1-butyl-3-methylimidazolium hydrogen sulfate [C₄C₁Im][HSO₄] ionic liquid. The addition of SiO₂ nano-filler results into enhancement in amorphicity and thermal stability and lowering of glass transition temperature of the membranes. A detailed investigation of possible interactions among the constituents PVA, [C₄C₁Im][HSO₄] and SiO₂, and cation–anion and anion–anion pairs of [C₄C₁Im][HSO₄] in the polymer electrolyte and their dissociation due to SiO₂ filler has been carried out in the membranes using Fourier transform infra-red (FTIR) and Raman spectroscopy. The membranes show maximum room temperature ionic conductivity as 9.9?×?10^?3 S cm^?1 for 6 wt.% of the nano-filler which is about four times higher than the membrane without nano-filler and an order higher than pure [C₄C₁Im][HSO₄]. With temperature, the ionic conductivity shows VTF behavior in the temperature range 40–120 °C. On the basis of FTIR and ion transport results, a model for ion transport in the membranes is proposed.

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Graphical abstract Schematic model of ion transport in nanocomposite polymer electrolyte membrane of PVA-[C₄C₁Im][HSO₄]-SiO₂

     

Synthesis and crystal structure of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(SeO<Subscript>4</Subscript>)] · 1.33H<Subscript>2</Subscript>O

The single crystals of Rb₂[(UO₂)₂(C₂O₄)₂(SeO₄)] · 1.33H₂O were synthesized and studied by X-ray diffraction. The crystals are monoclinic, space group P2₁/m, Z= 2, the unit cell parameters: a = 5.6537(8), b = 18.736(3), c = 9.4535(15) Å, β = 98.440(5)°, V = 990.6(3) ų, R ₁ = 0.0506. The main structural units of the crystal are infinite layers of [(UO₂)₂(C₂O₄)₂(SeO₄)]^2?, corresponding to the crystal chemical group A₂K ₂ ⁰² B² (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , B² = SeO ₄ ^2? ) of uranyl complexes. The uranium-containing layers are united into a three-dimensional framework through the electrostatic interactions with the outer-sphere rubidium ions and the hydrogen bonding system involving the outer-sphere water molecules.     

Reaction of the [B<Subscript>10</Subscript>H<Subscript>9</Subscript>O<Subscript>2</Subscript>C<Subscript>4</Subscript>H<Subscript>8</Subscript>]<Superscript>–</Superscript> anion with C-nucleophiles

The reactions of 1,4-dioxane-substituted closo-decaborate anion ([B₁₀H₉O₂C₄H₈]^–) with metal acetylenides, diethyl malonate, ethyl acetoacetate, triethyl orthoformate, acetylacetone, and malonodinitrile were studied. The reactions were shown to be accompanied with substituent ring opening and attachment of the corresponding pendant functional group. The obtained compounds were characterized by various physicochemical methods (IR and polynuclear NMR spectroscopy, ESI mass spectrometry).     

Crystal structure and thermal properties of [Au(en)<Subscript>2</Subscript>]<Subscript>2</Subscript>[Cu(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>]<Subscript>3</Subscript>·8H<Subscript>2</Subscript>O

The crystal structure of a double complex salt of the composition [Au(en)₂]₂[Cu(C₂O₄)₂]₃·8H₂O (en = ethylenediamine) at 150 K is determined by single crystal X-ray diffraction. The crystal data for C₂₀H₄₈Au₂Cu₃N₈O₃₂ are: a = 9.1761(3) Å, b = 16.9749(6) Å, c = 13.4475(5) Å, β = 104.333(1)°, V = 2029.43(12) ų, P2₁/c space group, Z = 2, d _x = 2.450 g/cm³. It is demonstrated that the thermal decomposition of the double complex salt in a helium or hydrogen atmosphere affords the solid solution Au_0.4Cu_0.6.     

Thermogravimetric analysis of wheatleyite Na<Subscript>2</Subscript>Cu<Superscript>2+</Superscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>·2H<Subscript>2</Subscript>O

Evidence for the existence of primitive life forms such as lichens and fungi can be based upon the formation of oxalates. These oxalates form as a film like deposit on rocks and other host matrices. The anhydrous oxalate mineral moolooite CuC₂O₄ as the natural copper(II) oxalate mineral is a classic example. Another example of a natural oxalate is the mineral wheatleyite Na₂Cu²⁺(C₂O₄)₂·2H₂O. High resolution thermogravimetry coupled to evolved gas mass spectrometry shows decomposition of wheatleyite at 255°C. Two higher temperature mass losses are observed at 324 and 349°C. Higher temperature mass losses are observed at 819, 833 and 857°C. These mass losses as confirmed by mass spectrometry are attributed to the decomposition of tennerite CuO. In comparison the thermal decomposition of moolooite takes place at 260°C. Evolved gas mass spectrometry for moolooite shows the gas lost at this temperature is carbon dioxide. No water evolution was observed, thus indicating the moolooite is the anhydrous copper(II) oxalate as compared to the synthetic compound which is the dihydrate.     

Study of Acidic (Tetracaprolactam) Dodecamolybdosilicate of the Composition (C<Subscript>6</Subscript>H<Subscript>11</Subscript>NO)<Subscript>4.5</Subscript>Н<Subscript>4</Subscript>[SiМо<Subscript>12</Subscript>O<Subscript>40</Subscript>]

New caprolactam dodecamolybdosilicate of the composition (C₆H₁₁NO)_4.5Н₄[SiМо₁₂O₄₀] (I) is synthesized. Chemical and crystallographic analyses, NMR and IR spectroscopic studies are performed. Compound I is found to crystallize in the monoclinic system with the space group P2₁/n. Unit cell parameters are: a = 19.945(4) Å, b = 13.340(3) Å, c = 28.110(6) Å, β = 110.75(3)°, ρ_calc = 2.232 g/cm³, М = 2350.63, Z = 4, V = 6994(3) ų.     

Synthesis and Crystal Structure of [Co(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>](C<Subscript>19</Subscript>H<Subscript>17</Subscript>O<Subscript>4</Subscript>SO<Subscript>3</Subscript>)<Subscript>2</Subscript>⋅8H<Subscript>2</Subscript>O

The title compound, cobalt 4′,7-diethoxylisoflavone-3′-sulfonate([Co(H₂O)₆](X)₂⋅8H₂O, X = C₁₉H₁₇O₄SO₃) was synthesized and its structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic space group P-1 with cell parameters a = 9.026(3) Å, b = 16.431(5) Å, c = 18.195(6) Å, α = 72.289(4)^∘, β = 87.498(4)^∘, γ = 82.775(5)^∘, V = 2550.1(13) Å⁻³, D_c = 1.419 Mg m⁻³, and Z = 2. The results show that the title compound consists of one cobalt cation, six coordinated water molecules, eight lattice water molecules, and two 4′,7-diethoxylisoflavone-3′-sulfonate anions, C₁₉H₁₇O₄SO⁻₃. Two anions have different conformations. Twelve H atoms of six coordinated water molecules, as donors, form hydrogen bonds with four oxygen atoms of sulfo-groups of two anions and eight oxygen atoms of eight lattice water molecules. In addition, π < eqid1 > ⋅ < eqid2 > π stacking interactions exist in the crystal structure, which together with hydrogen bonds lead to supramolecular formation with a three-dimensional network.     

The solubility of fullerene C<Subscript>60</Subscript>-fullerene C<Subscript>70</Subscript> mixtures in styrene at 25°C

The solubility of fullerene C₆₀-fullerene C₇₀ mixtures in styrene was studied under isothermal conditions at 25°C. The corresponding solubility isotherm is given and characterized.     

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

Synthesis and X-ray diffraction study of [UO₂CrO₄(C₅NH₅COO)] · H₂O crystals were performed. The compound crystallizes in the monoclinic system with the unit cell parameters a = 7.5025(3) Å, b = 11.5188(6) Å, c = 13.0518(6) Å, β = 97.877(4)°, V = 1117.29(9) ų, space group P2₁/n, Z = 4, R = 0.0263. The structure is formed by three [UO₂CrO₄(C₅NH₅COO)] layers parallel to (10\(\bar 1\)). The coordination polyhedron of uranium atoms is a pentagonal bipyramid, whose apices are occupied by oxygen atoms of uranyl, three chromate groups, and two molecules of isonicotinic acid. Crystal chemical formula of the [UO₂CrO₄(C₅NH₅COO)] layer can be represented as AT³B², where A = UO ₂ ²⁺ , T³ = CrO ₄ ^2? , and B² = C₅NH₅COO molecules. The isonicotinic acid molecules are in the form of zwitterions.     

Clathrate [Zn(C<Subscript>6</Subscript>H<Subscript>5</Subscript>COO)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 2CH<Subscript>3</Subscript>COOH: Synthesis and crystal structure

The clathrate [Zn(C₆H₅COO)₂(H₂O)₂] · 2CH₃COOH (I) was obtained for the first time from zinc(II) benzoate. The individuality, the unit cell parameters, and the number of “guest” molecules in complex I were determined from X-ray diffraction and derivatographic data. Its crystal structure was solved.     

Synthesis and examination of antimicrobial properties of aminomethylated derivatives C<Subscript>6</Subscript>–C<Subscript>7</Subscript> of alicyclic diols

Synthesis of C₆–C₇ alicyclic diols was studied by a catalytic oxidation of cyclohexene, norbornene and their methyl derivatives in the presence of heterogenized molybdenum-containing catalysts. By a triple condensation of the diols with formaldehyde and secondary amines a synthesis of their aminomethylated derivatives with various substituents at nitrogen atom was examined. Antimicrobial properties of the synthesized amino alcohols in M-10 oil as additives with fungicidal and bactericidal activities were studied.