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Journal of Structural Chemistry

2015 year, number 4

1.
CALCULATION OF CHARACTERISTICS OF THE ABSORBANCE OF FLUORIDES WITH REGARD TO MANY-PARTICLE EFFECTS

A. B. Gordienko, S. I. Filippov
Kemerovo State University, Kemerovo, Russia
Keywords: экситоны, фториды, химическая связь, электрон-дырочное взаимодействие, оптика, поглощение, метод моментов, KPM, excitons, fluorides, chemical bond, electron-hole interaction, optics, absorption, moment method, KPM

Abstract >>
A new approach to the solution of high dimension spectral problems, which is based on the use of the moment method (kernel polynomial method), is applied to study many-particle effects in a series of alkali fluorides. The electronic structure, absorption spectra, the features of the electronic charge distribution caused by the formation of bound electron-hole states and changes in these distributions in a series of fluorides due to distinctions in their electronic structure are analyzed.



2.
A DENSITY FUNCTIONAL THEORY ANALYSIS OF THE MOLECULAR HYDROGEN DISSOCIATION ON AlnPt (n = 1−12) CLUSTERS

X. An, L. Guo, N. Ren, C. Wen, X. Dong, S. Niu
Shanxi Normal University, Linfen, P. R. China
Keywords: AlnPt bimetallic cluster, hydrogen adsorption, DFT calculations, dissociation mechanism

Abstract >>
Bimetallic alloys are considered to be a promising type of catalysts with improved activity and selectivity that are distinct from those of the corresponding pure nanoclusters [1-4]. Using first principles density functional calculations, we study the structures and energies of AlnPt bimetallic clusters up to 13 atoms. If platinum, nickel, and other transition metal catalysts are particularly important in the catalysis of hydrogen, hydrogen adsorption on a metal surface is an important step in the catalytic reaction. Because of large exothermic energy changes and relatively small activation energies, Al7Pt and Al12Pt could serve as highly efficient and low-cost catalysts for the hydrogen dissociation. To clarify this assumption and achieve a good understanding, the H2 adsorption and dissociation over bimetallic AlPt clusters are systematically investigated in our work.



3.
FLUORESCENT TAGS. DANSYL AMIDE (CH3)2N−С10Н6−SO2NH2: REFLECTION OF THE CONFORMATIONAL PROPERTIES OF A FREE MOLECULE IN CRYSTAL STRUCTURES

N. I. Giricheva, E. A. Lapykina, M. S. Fedorov, D. A. Petrova
Ivanovo State University, Ivanovo, Russia
Keywords: дансиламид, конформеры, переходные состояния, NBO-анализ, квантово-химические расчеты, взаимосвязь структур кристалл-газ, dansyl amide, conformers, transition states, NBO analysis, quantum chemical calculation, crystal-gas structures interaction

Abstract >>
The conformational properties of a dansyl amide molecule (CH3)2N-C10Н6-SO2NH2, which is widely used for fluorescent labeling of compounds, e.g., amino acids or nucleotides and compounds able to form liquid crystals, are studied. It is found that the molecule has six conformers with relative energies 0/0.13, 1.13/1.38, 0.06/0.06, 0.31/0, 2.95/2.70, 0.31/0 (B3LYP/cc-pVTZ and МР2/cc-pVTZ methods respectively). In all conformers the naphthalene core becomes non-planar under the effect of two substituents. The effect of the nature of substituents on the geometric parameters of the conformers is considered. In terms of the NBO analysis a substantial deviation of the S-N bond in the -SO2NH2 substituent from orthogonality and also the asymmetrical position of the -N(СH3)2 group with respect to the naphthalene core are explained. The paths and barriers of conformational transformations of the dansyl amideа molecule are determined. The structure of the (CH3)2N-C10H6-SO2NН-X moiety in the crystals is analyzed and the relationship between the relative energy of the conformers of a free molecule and the probability of the occurrence of their structures in the crystals is determined.



4.
A THEORETICAL STUDY OF THE THERMAL CURTIUS REARRANGEMENT OF SOME CINNAMOYL AZIDES USING THE DFT APPROACH

Rafie H. Abu-Eittah1, Walid M.I. Hassan1, W. Zordok2
1University of Cairo, Giza, Egypt
2University of Zagazig, Zagazig, Egypt
Keywords: Curtius rearrangement, cinnamoyl azides, DFT treatment, one stage mechanism

Abstract >>
The thermal Curtius rearrangement of cinnamoyl azide, 1-azido-3-phenylprop-2-ene-1-one, and the reactions of some of its derivatives is studied theoretically using the DFT (B3LYP-631G(d, p) approach. The potential energy surface profiles of the rearrangement are calculated. The transition state was located and confirmed. The Curtius rearrangement of the studied compounds is a one-stage, discrete reaction. A weak effect of substitution on the reaction rate is due to the unique, localized p system of the studied molecules; strong opposing dipoles span the whole molecule.



5.
STRUCTURAL FEATURES OF COPPER FERRITE-CHROMITES

L. M. Plyasova1, V. I. Zaikovskii1,2, G. N. Kustova1, T. P. Minyukova1, I. Yu. Molina1, N. V. Shtertser1,2, T. M. Yurieva1
1Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: Cu-Fe-Cr шпинель, распределение катионов в структуре шпинели, структурный переход в шпинели, паровая конверсия СО, Cu-Fe-Cr spinel, distribution of cations in the spinel structure, structural transition in spinel, water gas shift reaction

Abstract >>
The structural features and the distribution of cations over crystallographic sites of copperchromite, copper ferrite, and mixed chromite-ferrites with the spinel structure obtained by thermal decomposition at 600°C and 900°C of mixed hydroxy compounds of copper, iron, and chromium with the composition Cu 2+/(Fe 3++Cr 3+) = 1/2 and different Fe 3+/Cr 3+ ratios are studied using a set of physicochemical methods. It is shown that the spinel-structure phases formed exist in two modifications: cubic and tetragonal, depending on the Fe 3+/Cr 3 ratio. The crystallographic relationship between the cubic and tetragonally distorted phases of spinel is analyzed. The distribution of cations over crystallographic sites, the character and degree of tetragonal distortion of Cu-Fe-Cr spinel depend on the Fe 3+/Cr 3+ ratio: when Fe 3+/Cr 3+ > 1, the ratio of unit cell parameters c */ а * > 1; when Fe 3+/Cr 3+ < 1, the ratio c */ а * < 1; when Fe 3+/Cr 3+ = 1, the spinel is cubic irrespective of the temperature of thermal treatment. The oxygen coordination of copper ions in the spinel structure has a significant effect on the catalytic properties of the samples in the low-temperature water gas shift reaction.



6.
PHASE TRANSITIONS AND IONIC MOBILITY IN SOLID SOLUTIONS IN THE BiF3−KF−ZrF4 SYSTEM

V. Ya. Kavun, E. B. Merkulov, M. M. Polyantsev, R. M. Yaroshenko, V. K. Goncharuk
Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok, Russia
Keywords: твердые растворы с флюоритовой структурой, ионная подвижность, фазовые переходы, спектры ЯМР 19F, спектры ДСК, рентгенофазовый анализ, solid solutions with a fluorite structure, ionic mobility, phase transitions, 19F NMR spectra, DSC spectra, X-ray crystallographic analysis

Abstract >>
The phase transitions and ionic mobility in solid solutions (SS) with the fluorite structure ((100−х)KBiF4−xZrF4, where х = 2.5−10 mol.%) are studied by DSC, X-ray crystallographic analysis, and 19F NMR methods. Phase transitions are determined in the solid solutions containing 10% of ZrF4. The types of ion motions in the SS fluoride sublattice and the corresponding temperature ranges (150−570 K) are determined. A high ionic conductivity in these solid solutions (~10-3−10-2 S/cm in the temperature range from 475 K to 550 K) is established, this fact not excluding the possibilities to use them for the production of materials with high ion conductive properties.



7.
CRYSTAL STRUCTURE, SPECTROSCOPIC AND MAGNETIC PROPERTIES OF A NEW IRON(III) COMPLEX

J. Abdelhak, S.N. Cherni, M.F. Zid, A. Driss
Universitй de Tunis, Tunis, Tunisie
Keywords: crystal structure, iron(III) complex, thermal behavior, visible and ultraviolet spectrometers, magnetic properties

Abstract >>
We report herein the synthesis and physicochemical characterization of a new mixed-ligand iron(III) complex of the formula (C<sub>5</sub>H<sub>6</sub>ClN<sub>2</sub>)[Fe(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]×2H<sub>2</sub>O. This compound is prepared by slow evaporation at room temperature and characterized by single crystal X-ray diffraction. It is characterized by IR and UV-VIS spectra and thermal analysis (TG and DTA). In this compound, the iron ion has a slightly distorted square bipyramidal environment, coordinated by two chelating oxalate ions and two water molecules. Structural cohesion is essentially established by p-p interactions between the rings of pyridine groups and intermolecular hydrogen bonds connecting the ionic entities and uncoordinated water molecules. Magnetic susceptibility measurements exhibit the paramagnetic behavior at high temperatures. However, at low temperatures, the magnetic data show the occurrence of weak antiferromagnetic intermolecular interactions between the local spins.



8.
EXPERIMENTAL AND THEORETICAL STUDIES ON THE SOLVATION OF POTASSIUM AND CHLORINE IONS IN AQUEOUS DIMETHYLSULFOXIDE SOLUTIONS

K. R. Grigoryan, A. A. Shilajyan, A. L. Zatikyan
Yerevan State University, Yerevan, Armenia
Keywords: вязкость, уравнение Джонса-Дола, В-коэффициент, диметилсульфоксид, ионы K+ и Cl, ab initio расчеты, SCRF расчеты, ион-молекулярные комплексы, viscosity, Jones-Dole equation, В-coefficient, dimethylsulfoxide, K+ and Cl ions, ab initio calculations, SCRF calculations, ion-molecular complexes

Abstract >>
Based on experimental (viscosimetric) studies, the physicochemical characteristics of solvated potassium and chlorine ions in dimethylsulfoxide-containing (DMSO) aqueous solutions are determined in the temperature range 25−40 °C. The Hartree−Fock nonempirical method (ab initio) with the (6−31+G(d,p)) basis set is used to calculate the structural and energy parameters of (K+,Cl)/H2O and (K+,Cl)/(H2O+DMSO) complexes in vacuum; the solvent effect is taken into account by the self-consistent reaction field (SCRF) method within the Onsager model. It is found that the solvation of individual ions in water−DMSO mixtures is due to the properties and structural features of the mixed solvent and the nature of the ions.



9.
THERMODYNAMICS AND STRUCTURE OF AQUEOUS ELECTROLYTE SOLUTIONS OF GLYCINE AT DIFFERENT TEMPERATURES

V. P. Korolev1, O. A. Antonova1,2, A. L. Serebryakova1,2
1Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
2Ivanovo State University of Chemistry and Technology, Ivanovo, Russia
Keywords: термодинамика, энтальпия растворения, параметры парного и тройного взаимодействия, двухкомпонентный растворитель, глицин, хлорид калия, хлорид натрия, мочевина, thermodynamics, enthalpy of dissolution, pair and triple interaction parameters, two-component solvent, glycine, potassium chloride, sodium chloride, urea

Abstract >>
The enthalpies of dissolution of glycine in aqueous electrolyte solutions are measured by calorimetry at temperatures of 288 K, 298 K, and 313 K in the molality range from 0.25 mol/kg to 6 mol/kg NaCl and to 4.5 mol/kg KCl. The enthalpy and heat capacity parameters are determined for the pair and triple interactions of glycine with electrolyte in water. Special (singular) points are discovered on the concentration dependences of the heats of dissolution of glycine in aqueous electrolyte solutions and in urea solutions at different temperatures. At these points, such a structurally sensitive property as the entropy of dissolution is temperature independent and the partial heat capacity of glycine is equal to that of the crystalline amino acid. The position of the singular point on the concentration axis is identical for NaCl and KCl solutions; in the case of urea solutions, the singular point is achieved at a much higher concentration of urea.



10.
NEW PRASEODYMIUM POLYSELENIDE PrSe1.95: SYNTHESIS AND X-RAY DIFFRACTION STUDY OF CRYSTALS

L. N. Zelenina1,2, T. P. Chusova1, N. V. Podberezskaya1, D. A. Piryazev1,2, I. V. Korolkov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: полиселениды празеодима, термодинамическое моделирование, выращивание кристаллов газотранспортным методом, рентгенофазовый и рентгеноструктурный анализ, praseodymium polyselenides, thermodynamic simulation, crystal growth by vapor transport, powder X-ray diffraction and single crystal X-ray diffraction study

Abstract >>
By thermodynamic simulation of the Pr−Se−I system, the optimal growth conditions for new crystalline praseodymium polyselenide PrSe1.95, whose existence was proved in our previous works, are determined. Based on the obtained information, the PrSe1.95 crystals are grown by the vapor transport technique using iodine as the transport agent. The crystals produced are identified by microprobe and powder X-ray diffraction analysis. Single crystal X-ray diffraction shows that the crystals are not monophasic, but consist of blocks with tetragonal and monoclinic symmetries, which have a common structural prototype (PbFCl). For two different crystals cut out of a larger one, the structure is determined and the composition is refined. The results of powder and single crystal X-ray diffraction analyses of one of these crystals (monoclinic one) coincide.



11.
CRYSTALLOGRAPHIC ANALYSIS AND FEATURES OF CATION COORDINATION IN A SERIES OF STRUCTURES OF SULFIDES WITH Tl+

S. V. Borisov, S. A. Magarill, N. V. Pervukhina
Nikolaev Institute of Inorganic Chemistry, Novosibirsk, Russia
Keywords: кристаллографический анализ, анионные "скелеты", катион Tl+ в сульфидах, координация Tl+, Tl+S-подрешетки, crystallographic analysis, anion skeletons, Tl+ cation in sulfides, Tl+ coordination, Tl+S sublattices

Abstract >>
A crystallographic analysis of ellisite Tl3AsS3, fangite Tl3AsS4, lorandite TlAsS2, and synthetic Tl3AsS3 shows that the configuration of atomic positions in these structures is determined mostly by the ordering of S2– anions and the large massive Tl+ cations in a single packing. The standard coordination of the As cation is provided only by the strong covalent As–S bonds; the environment of Tl+ cations varies depending on the geometry of their packing with sulfur.



12.
DETERMINATION OF THE CHEMICAL AND PHASE COMPOSITION MIXED WITH OKSIDOV PEROVSKITE STRUCTURES BASED ON STRONTIUM TITANATE METHOD OF DIFFERENTIATING DISSOLUTION

L. S. Dovlitova, D. V. Ivanov, L. A. Isupova, V. V. Malakhov
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: стехиография, метод дифференцирующего растворения, фазовый состав, композитные катализаторы, слоистые перовскиты, stoichiography, differential dissolution method, phase composition, composite catalysts, layered perovskites

Abstract >>
The results of the application of stoichiographic method of differential dissolution (DD) to analyze mixed oxides with the perovskite-like structure are presented. The samples of Sr1Ti0.9Mg0.1O3 with the ABO3 stoichiometry of perovskite and samples of Sr2Ti0.9Mg0.1O4 with the A2BO4 stoichiometry of layered perovskite (where A = Sr2+; B = Ti4+, Mg2+) are prepared by a mechanochemical method and analyzed before and after catalytic tests. Conditions of the detection, identification, and quantitative determination of different phases in the compositions of the samples are described. The surface comppositions of the initial samples are determined by the DD method, and changes observed after the catalytic tests are noted. The DD results are compared with the powder XRD results.



13.
ORIENTATIONAL DISORDER OF SULFATE IONS IN THE CRYSTAL STRUCTURE OF NH4Al0.43Fe0.57(SO4)2·12H2O

V. Kh. Sabirov
Kazakh Engineering and Pedagogical University of Nations Friendship, Shymkent, Republic of Kazakhstan
Keywords: квасцы, твердые растворы, запрещенные рентгеновские отражения, максимальные подгруппы, ориентационный беспорядок, alum, solid solutions, forbidden X-ray reflections, maximal subgroups, orientational disorder

Abstract >>
The crystal structure of the solid solution of alum NH4Al0.43Fe0.57(SO4)2×12H2O (I) is studied in the space group Ра3(-) and its maximal subgroups R3(-), P1(-), and P1. In centrosymmetric space groups sulfate ions occupy one of two opposite orientations, and in the triclinic group P1 four of eight tetrahedra have the same orientation. The second harmonic generation is observed when a train of chirped optical pulses of ytterbium diode pumped solid state laser passes through the crystal of I.



14.
MONO− AND BINUCLEAR Bi(III) IODIDE COMPLEXES CONTAINING 2,2'−BIPYRIDYL AND 1,10−PHENANTHROLINE: SYNTHESIS AND STRUCTURE

S. A. Adonin1,2, M. N. Sokolov1,2, V. P. Fedin1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: висмут, иодидные комплексы, 2,2'-бипиридил, 1,10-фенантролин, кристаллические структуры, bismuth, iodide complexes, 2,2'-bipyridyl, 1,10-phenanthroline, crystal structures

Abstract >>
Mononuclear complexes TBA[Bi(NN)I4] (TBA = tetra-n-butylammonium, NN = 2,2'-bipyridyl (1) and 1,10-phenanthroline (2)) are synthesized by the reaction of BiI3, tetra-n-butylammonium iodide, and the corresponding ligand in acetone with subsequent crystallization from a benzene-acetone mixture. By changing the solvent used in crystallization to ethanol, binuclear [Bi2(NN)2I6] complexes (3 and 4) are produced. The crystal structure of the compounds is determined by single crystal X-ray diffraction.



15.
CRYSTAL STRUCTURE AND THERMAL STABILITY OF NEW IRON PHOSPHATES KMFe(PO4)2 (M = Ni, Mg, and Co)

A. Badri1, M. Hidouri1, M.L. Lуpez2, M.L. Veiga2, C. Pico2, J. Darriet3, M.Ben Amara1
1Universitй de Monastir, Monastir, Tunisie
2Universidad Complutense, Madrid, Spain
3Institut de Chimie de la Matiиre Condensйe de Bordeaux, CNRS, Pessac-Cedex, France
Keywords: iron phosphates, synthesis, crystal structure, phase transitions, IR

Abstract >>
Three isostructural iron monophosphates KNiFe(PO4)2 (KNi), KMgFe(PO4)2 (KMg-LT, where LT means "low-temperature stable phase"), and KCoFe(PO4)2 (KCo-LT) are synthesized and structurally characterized from X-ray diffraction data. They crystallize in the monoclinic system with the space group P21/c. Their structures have in common a three-dimensional framework, built up by infinite zigzag chains of edge-sharing MO6 (M = Ni, Mg or Co) octahedra, linked by FeO5 and PO4 polyhedra via vertices and edges to form a rigid skeleton. The K+ ions are located in formed tunnels. DTA showed that KNi has a congruent melting at 941 °C, whereas KMg-LT and KCo-LT undergo irreversible phase transitions from P21/c to different high-temperature structures with the C2/c symmetry. IR absorption bands are assigned to different vibrations of the PO4 tetrahedron.



16.
A NEW 2D COBALT(II) COORDINATION POLYMER CONSTRUCTED FROM 1,2,4,5-BENZENETETRACARBOXYLATE AND FLEXIBLE bis(BENZIMIDAZOLE) LIGANDS

X. Du, R. Yang, X.X. Wang, G.H. Cui
Hebei United University, Tangshan, Hebei Province, P. R. China
Keywords: 1,2,3,4,5-benzenetetracarboxylate, bis(benzimidazole), cobalt(II), fluorescence property

Abstract >>
A new 2D cobalt(II) coordination polymers namely {[Co<sub>2</sub>(btec)(L)<sub>2</sub>]×4H<sub>2</sub>O}<sub><i>n</i></sub> (1), where btec = 1,2,4,5-benzenetetracarboxylate and L = 1,3-bis(5,6-dimethylbenzimidazol-l-yl)-2-propanol, are hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, and single crystal X-ray diffraction analyses. The structure analysis indicates that the compound belongs to the triclinic system, space group <i>P</i>ī, <i>a</i> = 12.198(2) Å, <i>b</i> = 15.0750(2) Å, <i>c</i> = 15.194(2) Å, α = 77.420(2)°, β = 77.872(2)°, γ = 85.538(2)°, <i>V</i> = 2664.2(5) Å<sup>3</sup>, <i>Z</i> = 2. The complex possesses a binodal (3,4)-connected two-dimensional layered structure bridged by btec and L ligands. The fluorescence and catalytic properties of the complex are also investigated.



17.
STRUCTURAL AND MASS SPECTROMETRIC CHARACTERISATION OF THE DINUCLEAR PLATINUM(II) SELENIDO-PHENYLSELENOLATO COMPLEX [Pt2(μ-Se)(μ-SePh)(PPh3)4]PF6

R.G. Fortney-Zirker, W. Henderson, B.K. Nicholson
University of Waikato, Hamilton, New Zealand
Keywords: platinum complexes, dinuclear complexes, selenide ligand, phenylselenolato ligand, arylation, crystal structure, electrospray mass spectrometry

Abstract >>
The reaction of [Pt2(μ-Se)2(PPh3)4] with diphenyliodonium bromide gave [Pt2(μ-Se)(μ-SePh)×(PPh3)4]+ through arylation of a selenide ligand. The complex is characterised by 31P NMR spectroscopy, elemental microanalysis, ESI mass spectrometry, and a single crystal X-ray diffraction study, which showed the four-membered {Pt2Se2} ring to be slightly puckered.



18.
LOCAL STRUCTURE OF SOLID SOLUTIONS FROM THE COMPUTER SIMULATION RESULTS AND EXPERIMENTAL DATA

V. S. Urusov†, N. N. Eremin
Moscow State University, Moscow, Russia
Keywords: атомистическое компьютерное моделирование, твердые растворы замещения, локальная структура, параметр релаксации, податливость позиции, межатомные расстояния, объемы полиэдров, atomistic computer simulation, solid substitution solutions, local structure, relaxation parameter, site compliance, interatomic distances, polyhedral volumes

Abstract >>
The possibilities of studying the local structure in isomorphic systems by methods based on the minimization of the interatomic interaction energy are considered in the work. The original procedure for the theoretical analysis of the local structure, which the authors have been developing for a number of years and have implemented in four computer programs, is discussed in detail. The practical implementation of this procedure is exemplified by the following solid substitution solutions: halite-sylvin (Na,K)Cl, corundum-eskolaite (Al,Cr)2O3, spinel-magnesiochromite Mg(Al,Cr)2O4, chrysoberyl-mariinskite Be(Al,Сr)2O4, grossular-uvarovite Ca3(Al,Cr)2[SiO4]3. Calculations are performed on a SKIF MGU Chebyshev supercomputer for supercells containing several thousands of atoms. The performed analysis of the behavior of changes in the geometric characteristics of CrO 6 octahedra in various isomorphic systems makes it possible to reveal the main reasons affecting the alteration of the relaxation parameter. It is found that the key factor is the size of the common structural unit of an isomorphic mixture. Thus, the behavior of the relaxation parameter obeys the isomorphism assistance rule.



19.
VARIATIONAL SOLUTION OF THE PROBLEM OF ANHARMONIC VIBRATIONS OF MOLECULES IN THE CENTRAL FORCE FIELD

L. A. Gribov1, N. I. Prokof’eva2
1Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, Moscow, Russia
2State University of Civil Engineering, Moscow, Russia
Keywords: колебания молекул, теория, ангармонизм, вариационный метод, molecular vibrations, theory, anharmonism, variational method

Abstract >>
A variational method of the solution of anharmonic problems in the theory of molecular vibrations in curvilinear coordinates (central force) with accurate taking into account the kinematic anharmonicity is proposed. The simplicity of computational procedures provides the application of this approach to the analysis of states of large molecules.



20.
IONIC MOBILITY AND PHASE TRANSITION IN HEPTAFLUORODIANTIMONATE(III) Cs0.4Rb0.6Sb2F7

V. Ya. Kavun1, M. M. Polyantsev1, L. A. Zemnukhova1,2
1Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok, Russia
2Far Eastern Federal University, Vladivostok, Russia
Keywords: гептафтородиантимонаты(III) цезия, рубидия, ионная подвижность, фазовый переход, ионная проводимость, спектры ЯМР 19F, ДСК, cesium-rubidium heptafluorodiantimonates(III), ionic mobility, phase transition, ionic conductivity, 19F NMR spectra, DSC

Abstract >>
The ionic mobility and conductivity in the crystalline phase of Cs0.4Rb0.6Sb2F7 (I) is studied using 19F NMR, DSC, and impedance spectroscopy methods. The analysis of the 19F NMR spectra makes it possible to follow the character of ion motions in the fluoride sublattice in the temperature range of 150−470 K, and to determine the types and temperature ranges of these motions. It is found that diffusion of fluorine ions becomes the dominant type of ion motions in the modification formed as a result of the reversible phase transition ( T = 415 K, the DSC data) in compound I. According to the preliminary results of electrophysical studies, the ionic conductivity in this compound is ~10-3 S/cm at temperatures above 450 K.



21.
TEMPERATURE DEPENDENCE OF THE SECOND OH OVERTONE ABSORPTION BAND OF VIBRATIONS OF THE WATER NEWLY MELTED IMMEDIATELY AFTER FREEZING

N. L. Lavrik1, E. V. Gornostaeva2
1Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: талая вода, сетка водородных связей, ИК спектры, melted water, hydrogen bond net, IR spectra

Abstract >>
The second overtone band shape of water and its temperature dependence are identical to those of melted and distilled water.



22.
CRYSTAL STRUCTURE OF Cs2[Mo10S10O10(OH)10(H2O)4](C4H2S(PO2H)2)·21H2O

D. S. Ogienko1, A. I. Smolentsev1,2, S. N. Konchenko1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: полиядерные комплексы, молибден, сера, фосфор, гетероциклические соединения, супрамолекулярные соединения, кристаллическая структура, polynuclear complexes, molybdenum, sulfur, phosphorus, heterocyclic compounds, supramolecular compounds, crystal structure

Abstract >>
We have determined the crystal structure of a supramolecular compound Cs2[Mo10S10O10(OH)10(H2O)4](C4H2S(PO2H)2)×21H2O comprising quasi-one-dimensional chains consisting of alternating cyclical [Mo10S10O10(OH)10(H2O)4] clusters and C4H2S(PO2H2)2 acid residuals of thiophene-2,5-diphosphonic acid hydrogen bonded with each other.



23.
CRYSTAL STRUCTURE OF THE SEVEN-ELECTRON MOLYBDENUM CLUSTER [MO3S4(DPPE)3CL3]·3.5C4H8O2·0.5ET2O

P. A. Petrov1,2, G. A. Sosnin2, D. Yu. Naumov1, S. N. Konchenko1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: кластерные комплексы, молибден, сера, рентгеноструктурный анализ, cluster complexes, molybdenum, sulfur, single crystal X-ray diffraction study

Abstract >>
The seven-electron neutral cluster complex [Mo3S4(dppe)3Cl3] (dppe = Ph2PCH2CH2PPh2) is obtained by the reduction of the [Mo3S4(dppe)3Cl3]Cl cluster with gallium metal. The molecular and crystal structure of [Mo3S4(dppe)3Cl3]×3.5C4H8O2×0.5Et2O solvate is determined by single crystal XRD. The crystallographic data are as follows: monoclinic crystal symmetry, space group C2/c, a = 41.1775(16) Å, b = 17.7178(7) Å, c = 28.9609(9) Å, β = 110.363(1)°, V = 19808.7(13) Å3, Z = 8, dcalc = 1.384 g/cm3.



24.
CRYSTAL STRUCTURE OF [PbCo(NO2)3(μ−OH)2]2

S. P. Khranenko1, N. V. Kuratieva1,2, A. V. Zadesenets1,2, S. A. Gromilov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: свинец, кобальт, рентгеноструктурный анализ, кристаллохимия, твердый раствор, сплав, lead, cobalt, single crystal X-ray diffraction study, crystal chemistry, solid solution, alloy

Abstract >>
The structure of [PbCo(NO2)3(μ-OH)2]2 is determined by single crystal X-ray diffraction. The geometric characteristics are analyzed and the packing motif is determined.



25.
NEW TRINUCLEAR μ3−VINYLIDENE CLUSTER CpReFePt(μ3−C=CHPh)(CO)5[P(OPri)3]2

V. V. Verpekin1, O. S. Chudin1, D. A. Piryazev2,3, A. I. Rubaylo1,4,5, S. A. Gromilov2,3, O. V. Semeikin6
1Institute of Chemistry and Chemical Technology, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russia
2Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
3Novosibirsk National Research State University, Novosibirsk, Russia
4Krasnoyarsk Scientific Center, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russia
5Siberian Federal University, Krasnoyarsk, Russia
6Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
Keywords: рений, железо, платина, винилиденовые комплексы, гетерометаллические комплексы, кластеры, рентгеноструктурный анали, rhenium, iron, platinum, vinylidene complexes, heterometallic complexes, clusters, single crystal X-ray diffraction study

Abstract >>
The X-ray diffraction study of a new heterometallic cluster CpReFePt(μ3-C=CHPh)(CO)5[P(OPri)3]2 is performed. The crystallographic characteristics are as follows: a = 11.0275(4) Å, b = 33.0367(12) Å, c = 12.2691(5) Å, β = 98.3660(10)°, V = 4422.2(3) Å3, space group P21/n , Z = 4, dcalc = 1.744 g/cm3. The cluster contains the phenylvinylidene ligand coordinated with a trimetallic core in the form of a Re-Fe-Pt chain (the Re-Fe and Fe-Pt bond lengths are 2.794(7) Å and 2.628(1) Å respectively; the Re∙∙∙Pt distance is 3.354(1) Å).



26.
CRYSTAL STRUCTURE OF A 3D Ag(I) COORDINATION POLYMER BASED ON FLEXIBLE BIS(BENZIMIDAZOLE) AND 5−NITROISOPHTHALIC ACID CO−LIGANDS

X. Zhang, L. Liu, L. Qin, G.H. Cui
Hebei United University, Tangshan, Hebei Province, P. R. China
Keywords: Ag(I) complex, 1,4-bis(5,6-dimethylbenzimidazol-1-yl)butane, crystal structure

Abstract >>
A new coordination polymer {[Ag4(L)3(nip)2](H2O)}n(L = 1,4-bis(5,6-dimethylbenzimidazol-1-yl)butane, H2nip = 5-nitroisophthalic acid) is hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. The complex features a 3D sqc117 supramolecular framework based on unique tetranuclear Ag(I) clusters which involve the ligand-supported Ag-Ag interactions.



27.
CRYSTAL STRUCTURE AND LUMINESCENT PROPERTIES OF A ONE-DIMENSIONAL Cd(II) COORDINATION POLYMER CONSTRUCTED BY 4,4'-DI-TERT-BUTYL-2,2'-BIPYRIDINE AND 5-TERT-BUTYL ISOPHTHALIC ACID

X.J. Xu, J. Wang
Yancheng Teachers University, Yancheng, Jiangsu, P.R. China
Keywords: Cd(II) complex, 4,4'-di-tert-butyl-2,2'-bipyridine, 5-tert-butyl isophthalic acid, crystal structure, luminescence

Abstract >>
A one-dimensional Cd(II) complex [Cd(Bu<sub>2</sub>bpy)(tbip)×H<sub>2</sub>O]<sub>n</sub> (1) (Bu<sub>2</sub>bpy = 4,4'-di-<i>tert</i>-butyl-2,2'-bipyridine, H<sub>2</sub>tbip = 5-<i>tert</i>-butyl isophthalic acid) is synthesized and characterized using single crystal X-ray diffraction, IR spectroscopy, and elemental analysis. The single crystal X-ray diffraction analysis reveals that complex 1 is a one-dimensional double chain polymer based on {Cd<sub>2</sub>(OCO)<sub>2</sub>} dimeric kernels with a Cd⋯Cd separation of 4.3197(7) Å. The thermal stability and luminescent properties of the title complex are briefly investigated.



28.
CRYSTAL AND MOLECULAR STRUCTURE OF [Au(C14H22N4)]ReO4

V. A. Afanasieva1, L. A. Glinskaya1, D. A. Piryazev1,2, S. A. Gromilov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: золото, рений, тетраазамакроцикл, комплексная соль, рентгеноструктурный анализ, рентгенофазовый анализ, кристаллохимия, термолиз, gold, rhenium, tetraazamacrocycle, complex salt, single crystal X-ray diffraction study, powder X-ray diffraction, crystal chemistry, thermolysis

Abstract >>
Perrhenate of the tetraazamacrocyclic complex of gold(III) [Au(C14H22N4)]ReO4 is synthesized. The crystal structure of the compound is determined by single crystal X-ray diffraction. The crystallographic data are as follows: а = 7.733(2) Å, b = 11.368(2) Å, c = 11.685(2) Å, α = 116.23°, β = 104.26°, γ = 94.96°; V = 870.3(3) Å3, space group P(-1), Z = 2, dcalc = 2.647 g/cm3, R = 0.0245. The packing of the complex is comprised of double stacks of cations and chains of anions linked into two-dimensional layers due to weak intermolecular interactions (non-classical hydrogen bonds C-H…O, C-H…Au, C-H…p and the Au…Au contacts). The thermal decomposition of the obtained compound in the hydrogen atmosphere is studied. According to the powder X-ray diffraction data, the product of the reduction of the synthesized salt is a mixture of nanocrystalline phases of Re and Au with the coherent-scattering regions of 17 nm and 13 nm respectively.



29.
CRYSTAL STRUCTURE OF THE CHAINED METAL-ORGANIC COORDINATION POLYMER [Cd(dmf)(ntca)]

I. S. Khan1,2, D. G. Samsonenko1,2, V. P. Fedin1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: кристаллическая структура, координационные полимеры, кадмий, crystal structure, coordination polymers, cadmium

Abstract >>
The crystal structure of a novel chained metal-organic coordination polymer [Cd(dmf)(ntca)] obtained by heating of cadmium nitrate and naphthalene-1,4,5,8-tetracarboxylic acid monoanhydride (H 2ntca) in N,N'-dimethylformamide (DMF) is determined.



30.
IODOBISMUTHATE COMPLEX (Bu4N)3[Bi3I12]: CRYSTAL STRUCTURE OF A NEW POLYMORPH

S. A. Adonin1,2, E. V. Peresypkina1,2, M. N. Sokolov1,2, V. P. Fedin1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: висмут, иодидные комплексы, полиморфизм, кристаллическая структура, bismuth, iodide complexes, polymorphism, crystal structure

Abstract >>
The structure of a new polymorph of the trinuclear iodobismuthate complex TBA3[Bi3I12] (TBA = tetra-n-butylammonium) (1) synthesized by the reaction of BiI3+TBA-I in the presence of silver triflate is identified.



31.
CRYSTAL STRUCTURE OF S,S'-DIMETHYL-N-NITROIMIDODITHIOCARBONATE

A. M. Astachov1, A. D. Vasiliev2, D. V. Antishin1, E. S. Buka1
1Siberian State Technological University, Krasnoyarsk, Russia
2Kirensky Institute of Physics, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russia
Keywords: нитримины, производные нитрогуанидина, рентгеноструктурный анализ, строение молекул, nitrimines, nitroguanidine derivatives, single crystal X-ray analysis, molecular structure

Abstract >>
The molecule of S,S'-dimethyl-N-nitroimidodithiocarbonate has a planar geometry (with the exception of hydrogen atoms of methyl groups), stabilized by the shortened S…O contact. The bond lengths in the >С=N-NO2 nitrimine moiety, in contrast to nitroguanidine derivatives, make it possible to consider the molecular structure of the compound within the traditional valence formula. The crystal structural feature of the compound is a low energy of its crystal lattice.



32.
CRYSTAL STRUCTURE OF 3-(2-(2-NITROPHENYL)HYDRAZONO)-5-PHENYL-3 H-FURAN-2-ONE

O. A. Maiorova1, V. S. Grinev2, A. Yu. Yegorova1
1Chernyshevsky National Research Saratov State University, Saratov, Russia
2Institute of Biochemistry and Physiology of Plants and Microorganism, Russian Academy of Sciences, Saratov, Russia
Keywords: рентгеноструктурный анализ, кристаллическая структура, азо-гидразо таутомерия, внутримолекулярная водородная связь, 3-(2-(2-нитрофенил)гидразоно)-5-фенил-3H-фуран-2-он, X-ray crystallographic analysis, crystal structure, azo-hydrazone tautomerism, intramolecular hydrogen bond, 3-(2-(2-nitrophenyl)hydrazono)-5-pheny-3H- furan-2-one

Abstract >>
The X-ray crystallographic method is used to determine the crystal structure and characteristic features of the molecular structure of 3-(2-(2-nitrophenyl)hydrazono)-5-phenyl-3 H-furan-2-one produced by the reaction of azo coupling of 2-nitrophenyldiazonium salt with 5-phenyl-3 Н-furan-2-one.



33.
FACILE SYNTHESIS AND CRYSTAL STRUCTURE OF 1,5-DIMETHYL-6-THIOXO-1,3,5-TRIAZINANE-2,4-DIONE

N. Shajari1, A.R. Kazemizadeh1, A. Ramazani1, S.W. Joo2, K. Ślepokura3, T. Lis3, A. Souldozi4
1Zanjan Branch, Islamic Azad University, Zanjan, Iran
2Yeungnam University, Gyeongsan, Republic of Korea
3University of Wrocław, Wrocław, Poland
4Urmia Branch, Islamic Azad University, Urmia, Iran
Keywords: N,N'-dimethylthiourea, trichloroacetyl isocyanate, triazinane, X-ray diffraction

Abstract >>
The title compound 1,5-dimethyl-6-thioxo-1,3,5-triazinane-2,4-dione C<sub>5</sub>H<sub>7</sub>N<sub>3</sub>O<sub>2</sub>S is synthesized via the reaction between N,N'-dimethylthiourea and trichloroacetyl isocyanate in dichloromethane. The structure of the title compound is characterized by IR, <sup>1</sup>HNMR, <sup>13</sup>C NMR, elemental analysis, and single-crystal X-ray diffraction. The crystal structure reveals the role of N-H⋯O and C-H⋯O hydrogen bonds, and C=O⋯π interactions in the arrangement of the molecules into ribbons, which are further joined to each other to form double-layers parallel to the (001) plane.