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Том 64, № 5 (2019)

Synthesis and Properties of Inorganic Compounds

Synthesis, X-ray Diffraction Studies, and Hydrogen Bonding Analysis of a New Phosphoramide Counterion in Solid State

Fallah N., Gholivand K., Yousefi M., Aberoomand azar P., Dusek M., Eigner V.

Аннотация

In the present study, we report the structure of one new phosphoramidate counter ion. The single crystal X-ray diffraction analysis revealed that C18H18N3O4P1, consists of a discrete [C18H18N2OP]+ cation and NO3 anion. The compound crystallizes in triclinic system, space group P-1, unit cell a = 9.4935 Å, b = 10.4556(4) Å, c = 11.1560(3) Å, α = 63.951(3)°, β = 67.039(3)°, γ = 66.017(3)°. The interaction between cation and anion has occurred through hydrogen bonding. The strength of different hydrogen bonds between two counter ions was studied by DFT calculations in the gas phase. We optimized the hydrogen atoms and kept all other atoms invariant in the optimization process. The H-optimized systems included one nitrate anion and one phosphoramide cation which were connected by special intermolecular interactions. The binding energies of these interactions were calculated (M062X/6-311G*) and corrected for the basis set superposition error (BSSE) using by counterpoise (CP) procedure. Moreover, the main noncovalent inter-molecular interactions were studied by Hirshfeld surface analysis and finger print plots.

Russian Journal of Inorganic Chemistry. 2019;64(5):557-564
pages 557-564 views

Layered Perovskite-Like Oxides LnSr2CuTiO6.5 (Ln = La, Nd, or Pr): Synthesis, Structure, and Dielectric Properties

Chupakhina T., Mel’nikova N., Kadyrova N., Deeva Y., Gyrdasova O.

Аннотация

Layered perovskite-like oxides LnSr2CuTiO6.5 (Ln = La, Nd, Pr) were prepared, of them, the Pr and Nd compounds were for the first time. Their crystal-chemical characteristics and dielectric properties were studied. The dielectric permeability of the compounds was shown to increase considerably after thermobaric treatment (TBT) due to the effects of temperature and high pressure on the anisotropy of interatomic distances in coordination polyhedra (Ln, Sr)O9, (Cu, Ti)O6, and (Ln, Sr)O12. All the oxides studied have an activation conductivity type.

Russian Journal of Inorganic Chemistry. 2019;64(5):565-573
pages 565-573 views

Characteristic Features of the Magnetic and Crystal Structure of the Hexagonal Ferrite BaFe12 − xInxO19

Korovushkin V., Trukhanov A., Shipko M., Kostishin V., Isaev I., Mironovich A., Trukhanov S.

Аннотация

The effect of the indium dopant on the magnetic properties and crystal structure of M-type barium hexaferrite was studied. Relying on Mössbauer spectroscopy data and magnetic measurements, the distribution of the dopant ions in the sublattices and their effect on magnetic characteristics were established. The dependences of specific magnetization and coercivity on the location of indium ions in the hexaferrite crystal structure and on the indium ion content were determined. Weakening of the exchange interaction between the sublattices at the replacement factor x = 0.6 and change in the magnetic moment orientation determined by the angle θ were revealed.

Russian Journal of Inorganic Chemistry. 2019;64(5):574-582
pages 574-582 views

Coordination Compounds

Structural Features of Monomeric Octahedral Monooxo d2-Rhenium(V) Complexes [ReO(Ln)2(Lmono)] with Oxygen Atoms of Bidentate Chelate O, N Ligands (Ln): 2. Complexes with Six-Membered Chelate Rings ReNC3O

Sergienko V.

Аннотация

The structural features of 24 mononuclear octahedral monooxo d2-Re(V) complexes with single charged oxygen atoms of bidentate chelate (O, N) ligands (Ln) of the general formula [ReO(Ln)2(Lmono)] (where Lmono is a monodentate ligand) containing six-membered chelate rings ReNC3O are discussed. The O(Ln) atoms, with three exception, are in the trans positions to the O(oxo) ligands. In the two complexes, the oxygen atoms of the acido-ligand OMe occupy the trans positions to the oxo ligands, and in the third, it is occupied by the O atom of the neutral H2O ligand. In the case of complexes [ReO(Ln)2(Lmono)] with five-membered chelate cycles ReNC2O, the structures of three complexes with Lmono ligands in the trans positions to oxo ligands are also known: one with Lmono = Cl and two with Lmono = OMe.

Russian Journal of Inorganic Chemistry. 2019;64(5):583-591
pages 583-591 views

Crystal Structure and Thermal Properties of Copper Complex with N-(2-Pyridyl)-2-Naphthoic Amide

Huang Q., Zhao Y., Wei X.

Аннотация

Complex Cu(SCN)2(CH3OH)2(NPNAA)2 (I) has been prepared by the reaction between Cu(OAc)2 with KSCN and the organic ligand N-(4-pyridyl)-2-naphthoic amide (NpNAA) by solvent evaporation method and structurally characterized by single-crystal X-ray diffraction. Complex I crystallizes in a triclinic system with space group \(P\overline 1 \). The three-dimensional solid-state structure of complex I is constructed by the strong π⋯π stacking effects between the bulky aromatic rings. The thermal properties of complex I have been investigated in air.

Russian Journal of Inorganic Chemistry. 2019;64(5):592-596
pages 592-596 views

Bis(μ3-2-oxybenzaldoximato-O, O′, N)-(μ2-oxo)-tetrakis(p-tolyl)diantimony, -tetrakis(3-fluorophenyl)diantimony, and -tetrakis(4-fhiorophenyl)diantimony: Synthesis and Structure

Sharutin V., Sharutina O., Efremov A., Artem’eva E.

Аннотация

The reactions of tris(p-tolyl)antimony, tris(3-fluorophenyl)antimony, and tris(4-fluorophenyl)antimony with 2-hydroxybenzaldoxime at equimolar amounts in diethyl ether in the presence of hydrogen peroxide have been studied. It has been established that 2-hydroxybenzaldoxime reacts as a bifunctional compound, and the simultaneous oxidation and dearylation of triarylantimony is observed. The products of these reactions are bis(μ3-2-oxybenzaldoximato-O, O′, N)-(μ2-oxo)-tetrakis(p-tolyl)-diantimony (I), -tetrakis(3-fluorophenyl)diantimony (II), and -tetrakis(4-fluorophenyl)diantimony (III), in which two structurally equivalent antimony atoms linked via two tridentate bridging ligands and an oxygen atom have a distorted octahedral coordination with the C2O3N surrounding according to X-ray diffraction study data. Their molecules have three types of Sb–O distances with the bridging oxygen atom (1.942(5), 1.946(5) Å in IA and IB, respectively, 1.948(3), 1.953(2) Å in II, and 1.954(3), 1.958(3) Å in III), the oxygen atoms of oxime groups (2.087(7) Å in IA and IB, 2.076(2), 2.097(2) Å in II, and 2.094(3), 2.081(3) Å in III), and the oxygen atoms of hydroxy groups (2.022(7), 2.024(7) Å in IA and IB, respectively, 2.002(3), 2.010(3) Å in II, and 2.015(4), 2.019(3) Å in III) and Sb⋯N coordination bonds (2.236(8), 2.238(9) Å in IA and IB, respectively, 2.256(3), 2.230(3) Å in II, and 2.266(4), 2.251(4) Å in III).

Russian Journal of Inorganic Chemistry. 2019;64(5):597-604
pages 597-604 views

Formation Reaction, Spectroscopy, and Photoelectrochemistry of the Donor–Acceptor Complex (5,10,15,20-Tetraphenyl-21,23H-porphinato)cobalt(II) with Pyridyl-Substituted Fullero[60]pyrrolidine

Bichan N., Ovchenkova E., Mozgova V., Kudryakova N., Lomova T.

Аннотация

Kinetic and thermodynamic parameters of the donor–acceptor self-organization in the system (5,10,15,20-tetraphenyl-21H,23H-porphyrinato)cobalt(II) (CoTPP)–1-methyl-2-(pyridin-4′-yl)-3,4-fullero[60]pyrrolidine (PyC60)–toluene yielding the 1: 2 complex (PyC60)2CoTPP are presented. The chemical structure of the supramolecular triad was elucidated by UV-vis, IR, and (1H, 13C) NMR spectroscopy. The photoelectrochemical characteristics of the Ti|TiO2 electrode modified by the triad and its precursors were determined and the redox behavior of the latter was studied by cyclic voltammetry in dichloromethane.

Russian Journal of Inorganic Chemistry. 2019;64(5):605-614
pages 605-614 views

Theoretical Inorganic Chemistry

Theoretical Modeling of the Structure and Stability of Complexes of the Icosahedral Al13 Ion with Borane and Alane Molecules

Charkin O.

Аннотация

The structures, energies, and spectroscopic characteristics of the \({\rm{A}}{{\rm{l}}_{13}}({\rm{B}}{{\rm{H}}_3})_n^-\) and \({\rm{A}}{{\rm{l}}_{13}}({\rm{Al}}{{\rm{H}}_3})_n^-\) complexes with the centered icosahedral aluminum cluster \({\rm{Al}}_{13}^-\) successively “solvated” with borane and alane molecules with n = 1–16 sequentially “solvated” with borane, alane, diborane, and dialane molecules (L = BH3, AlH3, B2H6, and Al2H6) have been calculated by the density functional theory (DFT) method. According to calculations, in the first half of the borane series \({\rm{A}}{{\rm{l}}_{13}}({\rm{B}}{{\rm{H}}_3})_n^-\), the BH3 molecules are coordinated to edges of the Al13 cage through two B–Al bonds and the B–Hb–Al hydrogen bridge. With increasing number of ligands n, B–Hb–B′ bridges between the ligands and binuclear B2Hm moieties with m = 3–5 appear in the surface region of the complexes. The calculations predicted the stability of borane complexes to decomposition with elimination of a diborane molecule and the possibility of their existence in the isolated state. In the early members of the alane series \({\rm{A}}{{\rm{l}}_{13}}({\rm{Al}}{{\rm{H}}_3})_n^-\), the ligands are also bound to the cage through two Al–Al′ bonds and a hydrogen bridge; with increasing n, they are even more prone than boranes to form H-bridges between the ligands and binuclear surface moieties Al2Hm. At n > 10, the internal cage is severely distorted and opened. At the end of the series, the cage changes its composition due to transfer of several Al atoms to the surface region. The alane complexes are less stable than their borane analogues; however, for the systems of the second half of the \({\rm{A}}{{\rm{l}}_{13}}({\rm{Al}}{{\rm{H}}_3})_n^-\) series, the calculations predict noticeable stability to decomposition with elimination of the dialane molecule. Trends in structural characteristics and energies of the complexes with increasing n are traced. The results can be of interest for modeling the structure and stability of more complicated nanosized aluminoborohydrides and aluminohydrides with high hydrogen content.

Russian Journal of Inorganic Chemistry. 2019;64(5):615-623
pages 615-623 views

Electron Density Redistribution in the System GeCl4←O=C[N(CH3)2]2 upon Coordination Bond Formation

Feshin V., Feshina E.

Аннотация

Quantum-chemical calculations of the system Cl4Ge←O=C[N(CH3)2]2 with full geometry optimization were performed by RHF/6-31G(d) and MP2/6-31G(d) methods. The calculations took into account that the Ge–Cl axial bond and the O=C bond are not at one line, as opposed to the previous belief. The MP2/6-31G(d) calculations of this system were also performed for various distances between coordination centers, and for GeCl4 and O=C[N(CH3)2]2 molecules, with full geometry optimization. The results of the calculations were used to quantify electron density redistribution in the system upon coordination bond formation. The electron density of chlorine atoms, especially, of the axial chlorine atom, was shown to increase upon coordination bond formation due to its transfer from the ligand hydrogen atoms and Ge–Cl bond polarization. The partial negative charge of the oxygen atom and the positive charge of the carbonyl carbon atom increase in association.

Russian Journal of Inorganic Chemistry. 2019;64(5):624-627
pages 624-627 views

Quantum-Chemical DFT Calculation of the Molecular Structures of “Template” Heteroligand (6666)Macrotetracyclic 3d M(II) Chelates with a 16-Membered Macrocyclic Ligand and Cl Ions

Chachkov D., Mikhailov O.

Аннотация

The geometries of (6666)macrotetracyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the NNNN coordination of the chelant donor sites, that can form through “self-assembling” in the MCl2–2-aminobenzenecarbaldehyde binary systems have been calculated by the DFT OPBE/TZVP method with the Gaussian 09 program package. The bond lengths and angles and nonbonded angles in these complexes with the MN4 chelate core have been determined. It has been demonstrated that neither the metal chelate core nor the six-membered chelate rings are strictly planar, although all the rings are identical or nearly identical to each other by the sets of bond angles. The noncoplanarity of the chelate rings is not pronounced (the deviation of the sum of the interior angles in each of them does not exceed 15°), the bond angles between the M–Cl bonds are 180°.

Russian Journal of Inorganic Chemistry. 2019;64(5):628-636
pages 628-636 views

Effect of 4d-Metal Impurities on the Electronic Properties of ZrO2 Nanotubes

D’yachkov E., D’yachkov P.

Аннотация

The electronic structure of ZrO2 nanotubes with 4d-metal impurities has been studied by quantum-chemical methods. The calculated densities of states with an impurity content of 4 at % demonstrate that partial replacement of Zr by Y, Nb, Tc, Ru, Rh, and Ag atoms leads to a decrease in the optical gap of (4,4) ZrO2 nanotubes from 3.7 to 1.5–2.2 eV owing to the broadening of band edges and formation of new peaks of density of states near the top of the valence band and the bottom of the conduction band of ZrO2. In these cases, doping ZrO2 leads to the displacement of absorption from the UV region to the visible range, and the nanotubes become promising materials for use as electrodes for sunlight-driven water photolysis.

Russian Journal of Inorganic Chemistry. 2019;64(5):637-640
pages 637-640 views

Physical Methods of Investigation

Thermochemistry of Nickel Trifluoride

Nikitin M., Alikhanyan A.

Аннотация

The literature data on thermal behavior of crystalline nickel fluorides NiF3 and Ni2F5 in the higher oxidation states are analyzed. Their enthalpies of formation are calculated: ΔfHo(Ni[NiF6](cr), 0 K) = -1399.6 ± 6 and ΔfHo(Ni2F5(cr), 0 K) = −1370.5 ± 8 kJ/mol. The partial saturated vapor pressures in the NiF3–Ni2F5 and Ni2F5–NiF2 systems over a broad temperature range are determined. The technical impossibility to achieve a measurable pressure of NiF3 is shown. The findings are compared to the data for similar derivatives of 3d-block elements and ruthenium and platinum trifluorides. Ni2F5(cr) is suggested to be used as a fluorine accumulator.

Russian Journal of Inorganic Chemistry. 2019;64(5):641-644
pages 641-644 views

Physicochemical Analysis of Inorganic Systems

Equilibrium Composition of Phases in Comelting of Natural Tecto-, Meta-, and Orthosilicates by the Example of Olivine Gabbronorite

Krenev V., Pechen’kina E., Fomichev S.

Аннотация

By the example of olivine gabbronorite, a basic plutonic rock of the gabbroid family, the effect of temperature and the redox properties of the crystallization atmosphere on the equilibrium composition of the formed phases was studied by physicochemical modeling. Brief data were presented on the chemical composition of the rock-forming minerals and their effect on the properties of the rock. Specific features of heating, melting, and crystallization of olivine gabbronorite were considered with taking into account the external conditions and the mutual influence of the minerals. The possibility of modifying the chemical and mineral compositions of olivine gabbronorite was shown. Recommendations were given on choosing a method for modifying the initial composition of olivine gabbronorite.

Russian Journal of Inorganic Chemistry. 2019;64(5):645-650
pages 645-650 views

Reactive Extraction of Zn and Cu with Bis(2-Ethylhexyl)Phosphate: Optimization using Taguchi Orthogonal Design

Sharma S., Agarwal G., Dutta N.

Аннотация

A comprehensive study on the reactive extraction of Zn and Cu has been established in an aqueous-organic two-phase system using bis(2-ethylhexyl)phosphate (HDEHP) to separate both the metals with the single extractant. Taguchi’s experimental design with orthogonal array L25 has been employed to evaluate the effect of most influencing parameters such as aqueous phase pH, carrier concentration, and contact time; experiments have been conducted accordingly. The optimum conditions have been obtained as following: aqueous phase pH 3.5 and 5.5 for Zn and Cu, respectively; carrier concentration, 15%; equilibrium time, 30 min. Under these optimum conditions, a quantitative extraction of Zn (91.8%) and Cu (90%) has been observed. Extraction equilibrium constant Keq has been estimated as 3 × 10−3 (mol/L)1/2 and 2.78 × 10−3 (mol/L)−1/2 for Zn and Cu, respectively. Herein, a complementary kinetic study has been also performed and the extraction process has been found to conform to the chemical reaction controlled mechanism.

Russian Journal of Inorganic Chemistry. 2019;64(5):651-660
pages 651-660 views

Solubility, Density, and Refractive Index in the Ternary System (K2B4O7 + Mg2B6O11 + H2O) at 298.15 K

Wang S., Zhao D., Song Y., Shi Z., Guo Y., Deng T.

Аннотация

Solubilities, densities, and refractive indices for the ternary system (K2B4O7 + Mg2B6O11 + H2O) at 298.15 K have obtained using the method of isothermal dissolution equilibrium. On the basis of the experimental data, the phase diagram and its corresponding physicochemical properties versus composition diagram in the system have been plotted. It has been found that there is one eutectic point and two crystallization regions corresponding to the large area of inderite (L + Mg2B6O11 · 15H2O) and the relative small area of potassium borate tetrahydrate (L + K2B4O7 · 4H2O), respectively. Neither double salt nor solid solution have been found in this system. The physicochemical properties (density and refractive index) of the ternary system at 298.15 K change regularly with the increasing of potassium borate concentration. The calculated values of density and refractive index using empirical equations of the ternary system are in good agreement with the experimental values.

Russian Journal of Inorganic Chemistry. 2019;64(5):661-665
pages 661-665 views

Physical Chemistry of Solutions

Extraction of Rare Earth Elements in 1,1,7-Trihydrododecafluoroheptanol–Water System with Phosphoryl Podands Derived from Diphosphonic Acids

Ivanova I., Krivorot’ko E., Ilyukhin A., Demin S., Pyatova E., Baulin V., Tsivadze A.

Аннотация

Extraction of rare earth elements (REE) in 1,1,7-trihydrododecafluoroheptanol–water system with phosphoryl podands derived from diphosphonic acids of general formula 2-[(HO)(EtO)(O)P]-4-Et–C6H3–(OCH2CH2)n–OC6H3-4-Et-2-[P(O)(OEt)(OH)], n = 1–5 has been studied. Effect of medium acidity on REE extraction efficiency and selectivity has been studied. Crystal structure of 1,5-bis[2-(oxyethoxyphosphoryl)phenoxy]-3-oxapentane has been established by X-ray diffraction.

Russian Journal of Inorganic Chemistry. 2019;64(5):666-672
pages 666-672 views

Inorganic Materials and Nanomaterials

Synthesis and Comparative Study of the Microstructure and Properties of LiNbO3 and LiNbO3:Zn Ceramics Manufactured by Sol–Gel Processes

Palatnikov M., Shcherbina O., Efremov V., Masloboeva S., Vladimirova S., Ivanenko D.

Аннотация

The manufacture of LiNbO3 and LiNbO3:Zn fine-grained powders by two variants of the sol–gel process was studied. The microstructure, mechanical and electric properties of LiNbO3 and LiNbO3:Zn ceramics prepared from powders of various origins were studied. The ceramics prepared from powders that had been fractionated by elutriation had uniform micro- and submicrostructure, improved strength characteristics, and ionic grain-boundary conductivity. Doping LiNbO3 with Zn2+ reduced the electronic conductivity of LiNbO3:Zn ceramics, and this allowed the ceramics to be efficiently polarized and their piezoelectric properties to be improved.

Russian Journal of Inorganic Chemistry. 2019;64(5):673-679
pages 673-679 views

Effect of Isovalent Doping by Zr4+ Ions on the Electrochemical Behavior of TiO2(B)

Opra D., Gnedenkov S., Sinebryukhov S., Ustinov A., Podgorbunsky A., Sokolov A.

Аннотация

In this study, TiO2(B) metastable β-TiO2 or bronze TiO2 was doped with Zr4+ (Zr/Ti = 0.03; 0.06) through hydrothermal approach. The materials were shown to be nanobelts (thickness: 10–l5 nm, width: 50–100 nm, length: several micrometers, and specific surface area: 72–76 m2/g). Doping the TiO2(B) structure with Zr4+ was found to be accompanied by the formation of Ti1−xZrxO2(B) (x = 0.03; 0.06) solid solutions, where the unit cell volume increases as the zirconium content rises. For doped TiO2(B), electrical conductivity increased by two order of magnitude, from 1.6 × 10−11 in an undoped sample to 8.2 × 10−10 S/cm for Zr/Ti = 0.06. After 90 charge/discharge cycles at the C/10-rate, Ti0.94Zr0.06O2(B) electrode had a capacity of 165 (mA h)/g. For undoped TiO2(B), this parameter was only 135 (mA h)/g. Moreover, Ti0.94Zr0.06O2(B) retained a reversible capacity of about 107 (mA h)/g even under an increased current load (5C). The major factors influencing the electrochemical behavior of Ti0.94Zr0.06O2(B) are the enhanced stability of the structure to lithiation/delithiation and an improved electrical conductivity.

Russian Journal of Inorganic Chemistry. 2019;64(5):680-687
pages 680-687 views