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2017 year, number 1

1.
A NEW METHOD OF SOLVING THE MANY-BODY SCHREDINGER EQUATION

V. M. Tapilin
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: многочастичное уравнение Шредингера, корреляция, He-подобные ионы, many-body Schrцdinger equation, correlation, He-like ions

Abstract >>
A new method of solving the many-body Schredinger equation is proposed. It is based on the use of constant particle-particle interaction potential surfaces (IPSs) and the representation of the many-body wave function in a configuration interaction form with coefficients depending on the total interaction potential. For these coefficients the corresponding set of linear ordinary differential equations is obtained. A hierarchy of approximations is developed for IPSs. The solution of a simple exactly solvable model and He-like ions proves that this method is more accurate than the conventional configuration interaction method and demonstrates a better convergence with increasing basis set.



2.
CHARACTERISTICS OF THE HYDROGEN BOND AND THE STRUCTURE OF Н-COMPLEXES OF p-n-PROPYLOXYBENZOIC ACID AND p-n-PROPYLOXY-p'-CYANOBIPHENYL

N. I. Giricheva, M. S. Fedorov, K. E. Shpilevaya, S. A. Syrbu, O. Yu. Ditsina
Ivanovo State University, Ivanovo, Russia
Keywords: жидкие кристаллы, п-н-пропилоксибензойная кислота, п-н-пропилокси-п'-цианобифенил, квантово-химические расчеты, NBO-анализ, конформеры, амплитуды колебаний, Н-комплексы, водородная связь, liquid crystals, p-n-propyloxybenzoic acid, p-n-propyloxy-pў-cyanobiphenyl, quantum chemical calculations, NBO analysis, conformers, vibrational amplitudes, Н-complexes, hydrogen bond

Abstract >>
The conformational properties of p-n-propyloxybenzoic acid and p-n-propyloxy- p'-cyanobiphenyl molecules, which can exhibit liquid crystalline properties in the formation of Н-complexes, are studied (DFT/B3LYP)/cc-pVTZ method). It is found that a molecule of p-n-propyloxybenzoic acid has 16 conformers that can be divided into four groups with respect to relative energies (0 kcal/mol, 1.6 kcal/mol, 6.5 kcal/mol, and 8.1 kcal/mol), and a molecule of p-n-propyloxy-p'-cyanobiphenyl has six conformers with relative energies of 0 kcal/mol (two conformers, φ(Сph-O-C-C)=180°) and 1.6 kcal/mol (four conformers, φ(Сph-O-C-C)=64.4°). In all conformers of the 3-AOCB molecule, phenyl rings are turned at 35° relative to each other. A conformation with the planar arrangement of two rings has a higher energy by 1.5 kcal/mol. Barriers to the internal rotation of different groups are determined and it is established that the structural nonrigidity of the molecules is mainly due to the possible rotation of the -C2Н5 moiety about the C-C bond. It is shown that with increasing temperature the vibrational amplitudes of the OC3H7 substituent, which enhance the probabilities of transitions between the conformers, become appreciably larger. It is found that p-n-propyloxybenzoic acid and p-n-propyloxy-p'-cyanobiphenyl can form Н-complexes with the medium hydrogen bond. Two types of the structural organization of Н-complexes are considered: linear and angular. The similarity of energies of Н-complexes with different structures (NBO analysis) can be the reason for the occurrence of two liquid crystalline subphases of p-n-propyloxybenzoic acid and p-n-propyloxy-p'-cyanobiphenyl system.



3.
QUANTUM CHEMICAL SIMULATION OF LOW-BASIC AN-221(НСl) ANION EXCHANGER DURING THE HYDRATION AND NON-EXCHANGEABLE ABSORPTION OF PHENYLALANINE

E. S. Trunaeva, O. N. Khokhlova, V. Yu. Khokhlov
Voronezh State University, Voronezh, Russia
Keywords: квантово-химическое моделирование, гидратация, фенилаланин, низкоосновный анионообменник, необменное поглощение, quantum chemical simulation, hydration, phenylalanine, low-basic anion exchanger, non-exchangeable absorption

Abstract >>
The formation of structures obtained during the hydration and non-exchangeable absorption of phenylalanine by a low-basic AN-221 ion exchanger in the НСl form is modeled in the work. Quantum chemical calculations are made using the Gaussian 03 program implementing the B3LYP hybrid density functional with the 6-31G++(d,p) basis set. The sequence of hydration and dissociation of functional groups of the ion exchanger is determined, the structure is optimized, and its formation energy during the non-exchangeable sorption of phenylalanine by the AN-221 (НСl) anion exchanger is estimated.



4.
ELECTRONIC STRUCTURE WITH A DIPOLE MOMENT CALCULATION OF THE LOW-LYING ELECTRONIC STATES OF THE KHe MOLECULE

S. Kontar, M. Korek
Beirut Arab University, Beirut, Lebanon
Keywords: ab initio calculation, KHe molecule, potential energy curves, spectroscopic constants, dipole moment

Abstract >>
The KHe molecular system is extensively studied by multi-reference configuration interaction calculations. Potential energy curves are constructed for 20 lowest electronic states, and molecular parameters are extracted. A comparison of our results with previous works shows remarkable agreement. A further calculation of the dipole moment functions through a wide range of the internuclear separation is performed and their corresponding curves are presented. Charge transfer is detected from the change in the sign of these functions particularly for R < Re. Negative dipole moment values near Re are predicted for 3 excited states, (1)2Π, (3)2+ and (1)4Π, which are of a relatively short-range strong-binding nature. On the other hand, weakly binding long-range excited states predict positive values of the dipole moment near Re reflecting the K-He+ polarity.



5.
A THEORETICAL STUDY OF THE SOLVENT EFFECT ON THE INTERACTION OF C20 AND N2H2

H. Alavi1, R. Ghiasi2
1Islamic Azad University, Kerman, Iran
2Islamic Qiam Azad University, Qiam Dasht, Iran
Keywords: C cage, C...NH molecules, frontier orbitals, solvent effect, hyperpolarizability

Abstract >>
In this work, the interaction of C20 and the N2H2 fragment is investigated at the M062X/6-311G(d,p) level of theory in both gas and solution phases. The interaction energies obtained by the standard method are corrected by the basis set superposition error (BSSE) during the geometry optimization for all molecules at the same levels of theory. The results obtained from these calculations reveal that the interaction between C20 and N2H2 increases in the presence of more polar solvents. Values of the electrophilic charge transfer show the charge flow from C20 to N2H2. The influence of the solvent on the hyperpolarizability indicates that btot values decrease on passing from vacuum to the solution phase.



6.
IR SPECTROSCOPY AND SINGLE CRYSTAL X-RAY DIFFRACTION STUDY OF 1,2-BIS(2-AMINOPHENOXY)-ETHANE, 1,5-BIS(2-AMINOPHENOXY)-3-OXAPENTANE, AND 1,8-BIS(2-AMINOPHENOXY)-3,6-DIOXAOCTANE

O. V. Koryakova1, M. L. Isenov1, E. S. Filatova1,2, O. V. Fedorova1,2
1Postovsky Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
2Ural Federal University, Ekaterinburg, Russia
Keywords: 1,2-бис(2-аминофенокси)-этан, 1,5-бис(2-аминофенокси)-3-оксапентан, 1,8-бис(2-аминофенокси)-3,6-диоксаоктан, ИК спектроскопия, РСА, 1,2-bis(2-aminophenoxy)-ethane, 1,5-bis(2-aminophenoxy)-3-oxapentane, 1,8-bis(2-aminophenoxy)-3,6-dioxaoctane, IR spectroscopy, XRD

Abstract >>
Vibrational spectra of 1,2-bis(2-aminophenoxy)-ethane, 1,5-bis(2-aminophenoxy)-3-oxapentane, and 1,8-bis(2-aminophenoxy)-3,6-dioxaoctane - podands, different in the length of oxyethylene fragments, are measured and their single crystal X-ray diffraction analysis is performed. It is demonstrated that the strength of intermolecular hydrogen bonds (IMHB) with the participation of NH groups increases with the elongation of the oxyethylene spacer. According to the XRD data for 1,2-bis(2-aminophenoxy)-ethane, the weakest hydrogen bonds are characteristic. From the IR spectra, important intermolecular hydrogen bonds are typical of 1,8-bis(2-aminophenoxy)-3,6-dioxaoctane having the longest oxyethylene fragment.



7.
LOCAL ATOMIC AND ELECTRONIC STRUCTURE OF QUANTUM DOTS BASED ON Mn- AND Co-DOPED ZnS

A. N. Kravtsova, A. P. Budnik, I. A. Pankin, T. A. Lastovina, A. L. Bugaev, L. D. Popov, M. A. Soldatov, V. V. Butova, A. V. Soldatov
International Research Center "Smart Materials", Rostov-on-Don, Russia
Keywords: квантовые точки, сульфид цинка, твердый раствор, атомная и электронная структура, компьютерное моделирование, XANES спектроскопия, quantum dots, zinc sulfide, solid solution, atomic and electronic structures, computer simulation, XANES spectroscopy

Abstract >>
Solid solutions of zinc sulfide with manganese and cobalt are synthesized. Based on the analysis of X-ray diffraction profiles the conclusion is drawn about the formation of a hexagonal wurtzite type structure in the synthesized quantum dot (QD) solutions. The average crystallite sizes are 8 nm and 22 nm for the samples with manganese and cobalt respectively. Results of IR and optical spectroscopy are consistent with the powder X-ray diffraction and X-ray fluorescence data. The question about particle aggregation in isopropanol and DMF solutions is considered. The QD structures based on ZnS particles doped with Mn and Co transition metal atoms are modeled. The possibility to apply X-ray absorption near edge structure (XANES) spectroscopy to verify the atomic structure parameters around the positions of doping transition metal atoms in QDs of the ZnS family is shown. Partial densities of ZnS:Mn and ZnS:Co electronic states are calculated.



8.
ADAPTATION WAYS FOR A HIGH CONCENTRATION OXYGEN VACANCIES IN NONSTOICHIOMETRIC STRONTIUM FERRITES

U. V. Ancharova1,2, S. V. Cherepanova3,2, S. A. Petrov1
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
3Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: гетерогенные твердые растворы на основе ферритов стронция, локальная структура, упорядочение вакансий, синхротронное излучение, рентгеновская дифракция, heterogeneous solid solutions based on strontium ferrites, local structure, vacancy ordering, synchrotron radiation, X-ray diffraction

Abstract >>
The structural analysis methods are used to study the features of the local structure of nonstoichiometric strontium ferrites with a high concentration of oxygen vacancies depending on the degree of substitution by highly charged cations and external conditions. The ways of their structure adaptation for the compositions with oxygen stoichiometry beyond the homogeneity regions of vacancy-ordered phases are suggested: it occurs via the formation of modulated one- and three-dimensional disordered nanostructures.



9.
STRUCTURAL, ELECTROSTATIC, AND THERMODYNAMIC PROPERTIES OF THE SURFACE OF SPHERICAL MICELLES IN SOLUTIONS OF SODIUM n-ALKYL SULFATE HOMOLOGUES. II. ELECTROSTATIC AND THERMODYNAMIC CHARACTERISTICS

V. S. Kuznetsov1, N. V. Usol’tseva1, A. P. Blinov1, N. V. Zharnikova1, A. I. Smirnova1, V. G. Badelin2
1Ivanovo State University, Ivanovo, Russia
2Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: ионные сферические мицеллы, электростатическая энергия, двойной электрический слой, межфазное натяжение, spherical ionic micelles, electrostatic energy, electric double layer, interfacial tension

Abstract >>
The structural characteristics of micelles from our previous work (Part I) are used to calculate the electrostatic energy of ions in the electric double layer on the surface of spherical ionic micelles in solutions of sodium n -alkyl sulfate homologues with the following number of carbon atoms in the molecule: nC = 8, 10, 12, and 14. This energy is found to depend on the thickness of the electric double layer and its average radius on the surface of a micelle, the aggregation number, the degree of binding of counterions, and the dielectric constant. The developed semi-empirical method is used to calculate interfacial tensions in spherical micelles for the said homologues in solutions at their critical micellar concentrations and T = 303 K. These values are split into the contributions from the hydrophobic and electrostatic components. The electrostatic component of the interfacial tension in spherical micelles is compared with the expression for the ion-ion repulsion energy to obtain the values of static permittivity (dielectric constant) in the surface layer of micelles.



10.
COMPETITION BETWEEN H2O AND CH3OH MOLECULES IN THE FORMATION OF THE SIMPLEST STABLE PROTON DISOLVATES AND THEIR SOLVATION IN AQUEOUS METHANOL SOLUTIONS OF KOH AND CH3OK

E. G. Tarakanova1, G. V. Yukhnevich1, I. S. Kislina2, V. D. Maiorov2
1Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
2Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, Russia
Keywords: водно-метанольные растворы, водородная связь, сольватация, дисольваты протона, строение H-связанных комплексов, KOH, CHOK, ИК спектры, квантово-химический расчет, aqueous methanol solutions, hydrogen bond, solvation, proton disolvates, structure of H-bonded complexes, KOH, CHOK, IR spectra, quantum chemical calculation

Abstract >>
IR spectroscopic and quantum chemical methods are used to study the competition between water and methanol molecules in the formation of the simplest stable proton disolvates and their subsequent solvation in the case of solutions of KOH in CH3OH and CH3OK in H2O with similar stoichiometries (~1:3-3.5). The complexes found in these solutions are analysed to determine their composition and structure: they are found to be heteroions (CH3O⋯H⋯OH)- solvated by two similar solvent molecules. In both cases, there are virtually no complexes of the second possible type (CH3OH×(CH3O⋯H⋯OCH3)-×H2O or CH3OH×(HO⋯H⋯OH)-×H2O), which appears to be due to the stoichiometric compositions of the solutions. It is shown that a DFT calculation (B3LYP/6-31++G(d,p)) of linear complexes with strong (~15-30 kcal/mol) H bonds reproduces, with good accuracy, the IR spectra of the solutions, which consist mainly of these complexes.



11.
CRYSTAL STRUCTURE OF NATURAL Ag-Cu-Pb-Bi SULFIDE

S. V. Borisov, N. V. Pervukhina, N. V. Kurat’eva, S. A. Magarill, B. M. Kuchumov
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: Ag-Cu-Pb-Bi-сульфид, структура, кристаллографический анализ, микродвойникование, катионные и анионные подрешетки, Ag-Cu-Pb-Bi sulfide, structure, crystallographic analysis, microtwinning, cation and anion sublattices

Abstract >>
The crystal structure of a natural sulfide Cu3,44Ag0,56Pb2Bi6S13 ( Сmcm , Z = 4, a = 3.973(1) Å, b = 13.370(2) Å, c = 42.182(7) Å, R = 0.059) is determined. The structure has seven cation positions: two of them (Cu and Ag) are in a tetrahedral environment of sulfur atoms; one (Pb), in a special position (mm2), has a coordination polyhedron in the form of a bicapped trigonal prism; and the other cation positions are surrounded by sulfur atoms forming distorted octahedra. The mirror symmetry plane perpendicular to the c translation causes microtwinning by cutting a layer of trigonal prisms framed by tetrahedron ribbons. These layers are divided by those composed by edge-linked octahedra with a diagonal ribbon of five octahedra ( N = 5). The cation and anion positions are ordered by individual sublattices with pseudohexagonal subcells on the m planes perpendicular to the a translation, which concentrate the positions of all the atoms. Supposedly, this natural sulfide is the previously described (1885) yet unconfirmed alaskaite mineral from the lillianite-heyrovskyite homological series and may be isostructural to the ourayite mineral.



12.
CRYSTAL STRUCTURES OF [RhL4Cl2][AuCl4] (L = Py, γ- AND β-PICOLINES) COMPLEX SALTS

D. B. Vasilchenko1,2, E. Yu. Semitut1,3, E. A. Bykova4, S. V. Korenev1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
3National Research Tomsk Polytechnic University, Tomsk, Russia
4University of Bayreuth, Bayreuth, Germany
Keywords: синтез, родий, пиридин, пиколин, золото, рентгеноструктурный анализ, synthesis, rhodium, pyridine, picoline, gold, single crystal X-ray diffraction analysis

Abstract >>
New double complex salts [RhL4Cl2][AuCl4] (L = Py, γ- and β-picolines) are synthesized. The compounds are characterized by elemental, powder and single crystal X-ray diffraction analyses. The salts crystallize in different space groups. A specific feature of the packing of [AuCl4]- complex anions is the chain formation due to additional Au…Cl or Cl…Cl contacts.



13.
CRYSTAL STRUCTURES OF [M(Еn)3](ReO4)2 (M = Ni, Zn)

S. P. Khranenko1, E. A. Bykova2, A. V. Zadesenets1,3, S. A. Gromilov1,3
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2University of Bayreuth, Bayreuth, Germany
3Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: никель, цинк, рений, этилендиамин, кристаллохимия, рентгеноструктурный анализ, nickel, zinc, rhenium, ethylenediamine, crystal chemistry, single crystal X-ray diffraction study

Abstract >>
The structures of two isostructural phases of [ M (Еn)3](ReO4)2 ( M = Ni, Zn; Еn is ethylenediamine) are studied. The crystal structures belong to the triclinic system, but demonstrate a pseudohexagonal packing motif. It is shown that the product of thermal decomposition of [Zn(Еn)3](ReO4)2 (hydrogen atmosphere, 400 °C) is a homogeneous mixture of nanocrystalline zinc and rhenium powders with coherent scattering regions of ~30 nm.



14.
CRYSTAL STRUCTURE OF FLUOROSULFATE COMPLEX COMPOUNDS OF INDIUM(III) M2[InF3(SO4)H2O] (M = K, NH4)

R. L. Davidovich1, V. B. Logvinova1, V. V. Tkachev2, G. V. Shilov2
1Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok, Russia
2Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia
Keywords: индий(III), смешанные лиганды, комплекс, сульфатофторидное соединение, полимерная цепь, кристаллическая структура, indium(III), mixed-ligand, complex, fluorosulfate compound, polymer chain, crystal structure

Abstract >>
The crystal structures of isostructural mixed-ligand fluorosulfate complex compounds of indium(III) M2[InF3(SO4)H2O] (M = K, NH4), formed of K+ cations, NH4+ respectively, and complex [InF3(SO4)H2O]2- anions are determined. In the complex anion, the indium atom surrounded by three F atoms, the oxygen atom of the coordinated H2O molecule, and two oxygen atoms of the bridging sulfate group forms a slightly distorted octahedron (CN 6). Via alternating bridging SO4 groups, the polyhedra of In(III) atoms are arranged in polymer chains. The O-H⋯F hydrogen bonds organize the chains in a three-dimensional network. The K+ and NH4+ cations are located in the structure framework and additionally strengthen it.



15.
CRYSTAL STRUCTURE OF A HYDROXO-BRIDGED DIMERIC URANYL COMPLEX WITH A 2,2':6',2"-TERPYRIDINE LIGAND

K. Lyczko, L. Steczek
Institute of Nuclear Chemistry and Technology, Warsaw, Poland
Keywords: uranyl complex, terpyridine, hydroxide bridge, crystal structure

Abstract >>
A new dimeric compound [{UO2(μ-OH)(terpy)}2](ClO4)2×0.67CH3CN, containing an uranyl cation and a tridentate 2,2':6',2"-terpyridine (terpy) ligand, is synthesized from an acetonitrile solution of uranyl perchlorate and terpy. The crystal structure of the compound is determined by single crystal X-ray diffraction. The crystal structure shows the formation of symmetric and asymmetric cationic hydroxo-bridged uranyl dimers. The uranium atoms adopt a distorted pentagonal bipyramidal configuration with a UO4N3 coordination environment formed by two uranyl O atoms, three N atoms from the terpy ligand, and two O atoms from the hydroxide anions.



16.
CRYSTAL AND MOLECULAR STRUCTURE OF THE DERIVATIVES OF PERCHLORATE (4Н-CHROMEN-4-YL) AND (9Н-XANTHENE-9-YL) TRIPHENYL PHOSPHONIUM

A. N. Utenyshev1, V. V. Tkachev1,2, N. S. Tkacheva1, A. A. Bumber†1
1Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region, Russia
2Institute of Physiological Active Compounds, Russian Academy of Sciences, Chernogolovka, Moscow Region, Russia
Keywords: рентгеноструктурное исследование, производные перхлората (9Н-ксантен-9-ил) и (4H-хромен-4-ил) трифенилфосфония, полиморфы, X-ray diffraction study, perchlorate (9Н-xanthene-9-yl) and (4H-chromen-4-yl) triphenyl phosphonium derivatives, polymorphs

Abstract >>
The X-ray diffraction study of new derivatives of perchlorate (9Н-xanthene-9-yl) and (4H-chromen-4-yl) triphenyl phosphonium is performed. It is demonstrated that the change in the molecular structure leading to a change in the degree of benzoannelation does not affect the phosphorus-carbon bond length. It is determined that perchlorate (2-phenyl-4Н-chromen-4-yl) triphenyl phosphonium сrystallizes as two polymorphs.



17.
STRUCTURE OF A BIMOLECULAR CRYSTAL OF 2,4,6,8,10,12-HEXANITRO-2,4,6,8,10,12-HEXAAZAISOWURTZITANE AND METHOXY-NNO-AZOXYMETHANE

I. N. Zyuzin, Z. G. Aliev, T. K. Goncharov, E. L. Ignatieva, S. M. Aldoshin
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia
Keywords: алкокси-NNO-азоксисоединения, метокси-NNO-азоксиметан, Z-2-метокси-1-метилдиазен 1-оксид, CL-20, бимолекулярные кристаллы, кристаллическая структура, alkoxy-NNO-azoxy compounds, methoxy-NNO-azoxymethane, Z-2-methoxy-1-methyldiazene 1-oxide, CL-20, bimolecular crystals, crystal structure

Abstract >>
The crystal structure of the bimolecular crystal of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and methoxy- NNO -azoxymethane (МАМ) (1:2) is studied. The CL-20 molecules adopt a z-conformation. The crystal structure is formed by layers of CL-20 and МАМ molecules, between which there are shortened NOd-⋯Nd+O contacts of the neighboring CL-20 and МАМ molecules.



18.
STRUCTURE AND ELEMENTAL COMPOSITION OF TRANSPARENT NANOCOMPOSITE SILICON OXYCARBONITRIDE FILMS

N. I. Fainer1, A. G. Plekhanov1, A. N. Golubenko†2, Yu. M. Rumyantsev1, E. A. Maksimovskii1, V. R. Shayapov1
1Nikolayev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: оксикарбонитрид кремния, нанокомпозитные пленки, 1,1,3,3-тетраметилдисилазан, плазмохимическое осаждение, silicon oxycarbonitride, nanocomposite films, 1,1,3,3-tetramethyldisilazane, plasma enhanced chemical vapor deposition

Abstract >>
Based on thermodynamic simulation data on the deposition of condensed phases with the complex composition in the Si-C-N-O-H system in a wide temperature range, using initial gas mixtures of 1,1,3,3-tetramethyldisilazane (HSi(CH3)2)2NH (TMDS), TMDS with a variable mixture of oxygen and nitrogen (O2+ xN2), a method is developed to obtain SiCxNyOz:H nanocomposite films by the plasma chemical decomposition of this gas mixture in the temperature range of 373-973 K. By FTIR and energy dispersive X-ray spectroscopy the structure of chemical bonds and the elemental composition of the obtained silicon oxycarbonitride films are studied. The in situ composition of the initial gas phase in PECVD processes is examined by optical emission spectroscopy.



19.
STRUCTURAL AND MORPHOLOGICAL PROPERTIES OF Ce1-xMxOy (M = Gd, La, Mg) SUPPORTS FOR THE CATALYSTS OF AUTOTHERMAL ETHANOL CONVERSION

M. A. Kerzhentsev1, E. V. Matus1, I. Z. Ismagilov1, V. A. Ushakov1, O. A. Stonkus1,2, T. V. Larina1, G. S. Kozlova3, P. Bharali4, Z. R. Ismagilov1,5
1Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
3Shared Research Center, Federal Research Center of Coal and Coal Chemistry, Siberian Branch, Russian Academy of Sciences, Kemerovo, Russia
4Tezpur University, Napaam, Tezpur Assam, India
5Institute of Coal Chemistry and Material Science, Federal Research Center of Coal and Coal Chemistry, Siberian Branch, Russian Academy of Sciences, Kemerovo, Russia
Keywords: диоксид церия, допирующие добавки, рентгенофазовый анализ, электронная микроскопия, электронная спектроскопия диффузного отражения, наноматериалы, cerium dioxide, dopants, powder XRD analysis, electron microscopy, electron spectroscopy of diffuse reflectance, nanomaterials

Abstract >>
A complex of physicochemical methods (powder XRD analysis, transmission and scanning electron microscopy, electron spectroscopy of diffuse reflectance, low-temperature nitrogen adsorption) is used for the comparative study of structural and morphological properties of oxide supports Ce1- x M x O y (M = Gd, La, Mg; x = 0-0.5; 1.5 ≤ y ≤ 2.0) for catalysts for the autothermal reforming of bioethanol to a hydrogen-bearing gas. It is shown that Ce1-x M x O y samples synthesized by the method of ester polymer precursors are mesoporous materials being the homogenous substitutional solid solutions with the fluorite-type cubic structure. The structural and textural properties of the Ce1-x M x O y materials are regulated by varying the type of the dopant cation (M = Gd, La, Mg), the molar ratio M/Ce (0, 0.1, 0.25, 1), and heat treatment conditions (temperature 300-800 °C; duration 4-24 h). The relationship between the synthesis parameters and the characteristics of the Ce1-x M x O y materials is found.



20.
FORMS OF SOLID SOLUTION ORDERING UPON DECREASING TEMPERATURE

S. K. Filatov1, A. P. Shablinskii1,2, S. N. Volkov2, R. S. Bubnova1,2
1St. Petersburg State University, St. Petersburg, Russia
2Institute of Chemistry of Silicates, Russian Academy of Sciences, St. Petersburg, Russia
Keywords: кристаллохимия, твердый раствор, порядок-беспорядок, расщепление позиций, сверхструктуры, модулированные структуры, тепловое движение атомов, ротационно-кристаллические состояния, crystal chemistry, solid solution, order-disorder, splitting of sites, superstructures, modulated structures, thermal atomic motion, rotational crystalline states

Abstract >>
The work reports different forms of solid solution ordering: from the well-known atom redistribution processes over positions and the decomposition of the solid solution to the formation of superstructures, modulated structures, rotation of atomic groups, splitting of sites. For each ordering form as a crystal chemical phenomenon the position of atoms, molecules, and vacancies in the crystal structure of the solid solution is considered and the place of these processes among the main crystal chemical phenomena is determined. The manifestation of order-disorder processes in phase diagrams of systems is also analyzed: from the classical heterogeneous decomposition of solid solutions to the formation of ordered chemical compounds and other phase transitions. The necessity of a thorough study of the atomic-molecular nature of the solid solution ordering by modern X-ray diffraction crystallographic methods and high-resolution electron microscopy is demonstrated. For each ordering form examples are given, the driving force of the process is distinguished, and a brief literature review is presented.



21.
HELIUM, NEON, AND WATER

G. G. Malenkov
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russia
Keywords: гелий и неон в воде, водных пленках, пленках льда II, молекулярная динамика, helium and neon in water, water films, ice II films, molecular dynamics

Abstract >>
The molecular dynamics method is used to study liquid aqueous solutions of helium and neon, liquid water films and solid films with an ice II structure in helium and neon atmospheres, and solid solutions of helium and neon in ice II. Gas atoms wander randomly in water and make occasional slow jumps. The structure of the hydrate shell of the gas atoms bears little resemblance to the structure of ice II and other ice modifications. The solubility of neon in a water film is only a little higher than that of helium. Helium and neon atoms that find themselves in the channels of a thin ice II film make the same jumps along the channels as those along the channels in the structure of ice II crystals. The motions of two neon atoms in the neighboring (along the z axis) planes are correlated, whereas there is no correlation between the motions of helium atoms.



22.
SOLVENT EFFECTS ON THE NH STRETCHING OF 1-(4-PYRIDYL)PIPERAZINE

C. Parlak
Ege University, Izmir, Turkey
Keywords: 1-(4-pyridyl)piperazine, DFT, NH stretching, solvent effect

Abstract >>
The solvent effects on the NH stretching of 1-(4-pyridyl)piperazine (1-4pypp, C9H13N3) are investigated by density functional theory (DFT). The B3LYP hybrid density functional is used with the 6-311+G(3df,p) basis set in the polarizable continuum model (PCM). Computations are performed with 18 different polar or non-polar solvents. The calculated frequencies of the solvent-induced NH stretching vibrations are correlated with some solvent parameters such as the Kirkwood-Bauer-Magat (KBM) equation, the solvent acceptor number (AN), Swain parameters, and the linear solvation energy relationships (LSER). The present work explores the effects of the medium on the n(NH) vibrations. The findings of this research can be useful for piperazines.



23.
CHEMICAL SHIELDING OF DOPED NITROGEN ON C20 CAGE AND BOWL FULLERENES

F. R. Nikmaram, A. Khoddamzadeh
Islamic Azad University, Tehran, Iran
Keywords: C (cage), C (bowl), nitrogen doping, NMR

Abstract >>
The C20 (cage), C20 (bowl), C20H10 (bowl) fullerene structures and their nitrogen doped derivatives such as C20NH (cage), C20NH (bowl), C20H10N (bowl), C20H10NH (bowl) are fully optimized at the MPW1PW91/6-31G level of theory. The natural atomic charge comparison shows that in C20H10N (bowl), the nitrogen atom with about -0.58 has a more negative charge with respect to other nitrogen doped structures. The nuclear magnetic resonance chemical shielding is evaluated for nitrogen doped structures and the neighbors connected to nitrogen, C6, and C7 atoms. The nitrogen atom doped on carbon sites of C20H10N (bowl) has the largest shielding isotropic shifts to the upper field (-203.58 ppm). This means that the electron density around nitrogen in the C20H10N (bowl) structure is higher. Interestingly, there is a significant correlation between the charges and siso values of nitrogen and carbon atoms (C6 and C7). Namely, as the charge becomes more negative, siso shifts to the upper field. It is predicted that nitrogen doped C20H10N (bowl) with the maximum electron density adopts this structure for electrophilic reactions.



24.
ZINC HALIDE COMPLEXES OF THIONICOTINAMIDE; CRYSTAL STRUCTURE OF DICHLORIDO BIS(THIONICOTINAMIDE-kN)ZINC(II)

M. Akhtar1, M. R. Malik1, M. N. Tahir2, S. Nadeem1, M. Altaf3, M. Sohail3, S. Ali1, S. Ahmad4
1Quaid-i-Azam University, Islamabad, Pakistan
2University of Sargodha, Sargodha, Pakistan
3King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
4Prince Sattam bin Abdulaziz University, Al-Kharj, Saudi Arabia
Keywords: zinc(II), thionicotinamide, NMR spectroscopy, crystal structure

Abstract >>
Zinc halide complexes of thionicotinamide (TNA) having the general formula [Zn(TNA)2X2] (X = Cl-, Br-, I-) are prepared and characterized by thermal analysis, IR and NMR spectroscopy. The crystal structure of one of them, dichloridobis(thionicotinamide-kN)zinc(II), [Zn(TNA)2Cl2] (1), is determined using X-ray crystallography. In 1, the zinc atom is coordinated by two thionicotinamide ligands through nitrogen atoms and two chloride ions in a distorted tetrahedral coordination environment. The molecular structure of the complex is stabilized through intermolecular hydrogen bonding.



25.
CRYSTAL STRUCTURE OF SYNTHETIC VOLTAITE (K0.90(NH4)0.10)2(Fe3,1902+Fe1,1243+Mg1,686)(Fe0,9383+Mg0,062)2(Al0,98Fe0,023+)(SO4)12x18.9H2O

V. Kh. Sabirov
Ayezov South Kazakhstan State University, Shymkent, Kazakhstan
Keywords: вольтаит, каркасная структура, изовалентное и гетеровалентное замещения, октаэдрическая координация, voltaite, framework structure, isovalent and heterovalent substitutions, octahedral coordination

Abstract >>
Voltaite of the composition [K0.90(NH4)0.10]2(Fe3,1902+Fe1,1243+Mg1,686)(Fe0,9383+Mg0,062)2(Al0,98Fe0,023+)×(SO4)12x18.9H2O is obtained by treating a polymetallic sample with sulfuric acid. The crystal structure of the substance is formed of (Fe3+,Mg)O6 and (Fe2+,Fe3+,Mg)O4(H2O)2 octahedra and a (K+,NH4+)O12x12-vertex polyhedron arranged in a three-dimensional framework due to the bridging function of the SO42- ion. In the framework voids, [(Fe3+,Al)(H2O)6]3+ cations with aqua ligands disordered over several positions are located.



26.
CRYSTAL STRUCTURE, ELECTROCHEMICAL AND MAGNETIC PROPERTIES OF A NEW BINUCLEAR COPPER(II) COMPLEX WITH BENZOIC ACID AS A LIGAND

W. Lu, S.-L. Yang, L. Xu, X.-W. Chi, Y.-Y. Xu, H.-J. Sun
Nanjing Forestry University, Nanjing, P. R. China
Keywords: synthesis, copper(II) complex, crystal structure, electrochemical and magnetic properties

Abstract >>
A new complex [Cu2(L)4(DMF)2] (1) with benzoic acid (HL) as a ligand is synthesized by the solid phase synthesis method. Crystal data for the complex are as follows: monoclinic, space group P21/n, a = 10.593(2) Å, b = 10.123(2) Å, c = 16.336(3) Å, β = 93.55(3)°, V = 1748.4(6) Å3, Dc = 1.439 g/cm-3, Z = 4, F (000) = 780, GOOF = 1.003, final discrepancy factors R1 = 0.0624, wR2 = 0.1559. In 1, the Cu(II) ion is coordinated by six atoms to give a distorted octahedral coordination geometry. The electrochemical, fluorescent, and magnetic properties of 1 are studied. The results show that the electron transfer of 1 is quasi reversible in the electrode reaction corresponding to Cu(II)/Cu(I), and 1 exhibits three relatively strong fluorescent emission peaks at 403, 425, and 454 nm. In addition, complex 1 displays the antiferromagnetic property in a temperature range of 300 ~ 10 K.



27.
STRUCTURAL CHARACTERIZATION OF A NEW METALLOPOLYMER COMPLEX OF 1,10-PHENANTHROLINE AND NITRATE [Cu(C12H8N2)(NO3)2]n

S. N. Cherni, A. Driss
Crystal Chemistry and Materials Laboratory, Tunis, Tunisia
Keywords: mixed-ligand copper(II) complex, X-ray diffraction, π⋯π stacking interactions, five-coordination of Cu(II), zigzag polymeric chain complex

Abstract >>
A new mixed-ligand copper(II) complex of 1,10-phenanthroline and nitrate ligands [Cu(C12H8N2)(NO3)2] n is prepared and its crystal structure is determined by X-ray diffraction. The complex crystallizes in the monoclinic space group P21/n, with unit cell dimensions a = 8.8226(3) Å, b = 9.1462(1) Å, c = 17.2507(4) Å, β = 101.680(2)°, Z = 4, V = 1363.19(6) Å3. The crystal structure is solved by the Patterson method and refined by full-matrix least squares treatment on F 2 to final values R1 = 0.0447 and wR2 = 0.1053. The CuII ions are five-coordinated in a CuO3N2 environment, giving a distorted square-based pyramidal geometry. The Cu…Cu distance in the [Cu(C12H8N2)(NO3)2] n zigzag polymeric chain is 5.258(1) Å. The structure of the title compound is polymeric and consists of layers running parallel to (101), interconnected by π-π interactions, strong enough to form a three-dimensional framework with tunnels along the a axis.



28.
CRYSTAL STRUCTURE OF IRIDIUM(III) ACETYLACETONATE COMPLEXES BEARING AXIAL BROMIDE-SUBSTITUTED PYRIDINE

Q.-W. Chang, H. Cui, C.-X. Yan, J. Jiang, Q.-S. Ye, J. Yu, J.-L. Chen, W.-P. Liu
Kunming Institute of Precious Metals, Kunming, P.R. China
Keywords: iridium, acetylacetone, 3-bromopyridine, 4-bromopyridine, crystal structure

Abstract >>
Two iridium acetylacetonate complexes bearing axial bromide-substituted pyridine (3-bromopyridine, 1 and 4-bromopyridine, 2) are synthesized and their crystal structures are determined by single crystal X-ray diffraction. In both complexes, a distorted octahedral geometry of the central Ir(III) atom is formed by four oxygen atoms of two acetylacetone ligands, a carbon atom of one acetylacetone ligand, and a nitrogen atom of bromide-substituted pyridine.



29.
CRYSTAL STRUCTURE OF HETEROMETALLIC CLUSTER COMPOUNDS K5.3RB0.7[RE3MO3S8(CN)5] AND K4.4CS1.6[RE3MO3S8(CN)5]

Ya. M. Gayfulin1, A. I. Smolentsev1,2, Yu. V. Mironov1,2, N. G. Naumov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: синтез, рений, молибден, гетерометаллический кластерный комплекс, полимер, кристаллическая структура, synthesis, rhenium, molybdenum, heterometallic cluster complex, polymer, crystal structure

Abstract >>
Rhenium-molybdenum cluster compounds K5.3Rb0.7[Re3Mo3S8(CN)5] (1) and K4.4Cs1.6[Re3Mo3S8(CN)5] (2) are obtained by the interaction of an equimolar mixture of ReS2 and MoS2 with molten KCN and RbI/CsCl, respectively. The structure of the complexes is determined by the XRD method. The compounds crystallize in the tetragonal crystal system, space group I4/m. The crystal structure is composed of anionic chains of [Re3Mo3S8(CN)4(CN)2/2]6- aligned along the a crystallographic axis and M+ cations located in voids of the lattice. The effect of additional Cs+ and Rb+ cations on the crystallographic parameters and geometric characteristics of the clusters is analyzed.



30.
MIXED-LIGAND FLUOROOXALATE COMPLEX COMPOUNDS OF INDIUM(III) M2[InF3(C2O4)H2O] (M = K, Rb): SYNTHESIS AND CRYSTAL STRUCTURE

R. L. Davidovich1, V. B. Logvinova1, V. V. Tkachev2, G. V. Shilov2
1Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok, Russia
2Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia
Keywords: индий(III), смешанные лиганды, оксалатофторидное комплексное соединение, синтез, полимерная цепь, кристаллическая структура, indium(III), mixed-ligand, fluorooxalate complex compound, synthesis, polymer chain, crystal structure

Abstract >>
Isostructural fluorooxalate complex compounds of indium(III) M2[InF3(C2O4)H2O] (M = K, Rb), being the first representatives of a new class of mixed-ligand fluoro-containing complex compounds of indium(III) are synthesized for the first time and structurally studied. The crystal structures of M2[InF3(C2O4)H2O] (M = K, Rb) are formed of K+ cations (Rb+ respectively) and complex [InF3(C2O4)H2O]2- anions. The indium atom in the complex anion is surrounded by four F atoms, two of which are bridging, the oxygen atom of the coordinated H2O molecule, and two oxygen atoms of the bis-bidentate (tetradentate) oxalate group. The coordination polyhedron of the indium atom (CN 7) is a pentagonal bipyramid. Via alternating double bridging F atoms and tetradentate bridging C2O4 group, the In(III) atom polyhedra are arranged in polymer chains. Via hydrogen O-H⋯F bonds the chains are organized in layers. Between the layers, the K+ or Rb+ cations are located, which strengthen the crystal structure.



31.
CRYSTAL STRUCTURE AND THEORETICAL CALCULATIONS OF 1-(4-TRIFLUOROMETHYL-2,3,5,6-TETRAFLUOROPHENYL)-3-BENZYLIMIDAZOLIUM BROMIDE

G. C. Saunders, H. P. Thomas
University of Waikato, Hamilton, New Zealand
Keywords: imidazolium, anion-πinteraction, X-ray structure

Abstract >>
The salt 1-(4-trifluoromethyl-2,3,5,6-tetrafluorophenyl)-3-benzylimidazolium bromide [(CF3C6F4)NC3H3N(CH2Ph)]+×Br- is crystallized from methanol in the space group P-421c of the tetragonal crystal system with unit cell parameters a = b = 21.6531(3) Å, c = 8.1968(2) Å, V = 3843.13(13) Å3, Z = 8, dcalc = 1.5732 g/cm-3. The structure possesses square channels with a width of ca. 5.2 Å, which accounts for 14 % of the volume, and contains one methanol molecule per ion pair. The cation interacts with three bromide ions through an anion - π interaction and two C-H⋯Br- interactions. These interactions are investigated by DFT calculations.