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Journal of Structural Chemistry

2016 year, number 4

1.
ATOMIC STRUCTURE OF THE HIGHER MOLECULAR ORBITALS OF SMALL TETRA-HEME CYTOCHROME WITH 1M1P

A.V. Mitin1,2,3
1Moscow State University, Moscow, Russia
2National Research Center "Kurchatov Institute", Moscow, Russia
3Moscow Physical Technical Institute, Dolgoprudnyi, Moscow region, Russia
Keywords: неэмпирический расчет, приближение ЛКАО, метод Хартри-Фока, молекулярные орбитали, анализ заселенности, non-empirical calculation, LCAO approximation, Hartree-Fock method, molecular orbitals, population analysis

Abstract >>
The atomic structure of the higher molecular orbitals (MO) of small tetra-heme cytochrome (STC) with 1M1P is studied in large non-empirical calculations performed by the Hartree-Fock method with taking into account all electrons. It is shown that the higher MO of STC are mainly formed by atomic orbitals of negatively charged amino acid atoms. The corresponding amino acids and their numbers are determined. The conclusion is drawn that these amino acids can be considered as possible active centers in the electron transfer reaction from STC to the external electron acceptor.



2.
OPTICAL TRANSITIONS WITH CHARGE TRANSFER IN SUPRAMOLECULAR FULLERENE AND PORPHYRIN COMPOUNDS IN THE CRYSTALLINE STATE

P.O. Krasnov1,2, A.A. Kuzubov2, A.S. Kholtobina2, E.A. Kovaleva2, M.V. Kuzubova2
1Siberian State Technological University, Krasnoyarsk, Russia
2Siberian Federal University, Krasnoyarsk, Russia
Keywords: фотогальванические элементы, квантово-химические расчеты, теория функционала плотности, DFPT, дисперсионное взаимодействие, photogalvanic elements, quantum chemical calculations, density functional theory, dispersion interaction

Abstract >>
By the DFT method with the planar wave basis set and in the PAW approximation the geometric and electronic structures of four supramolecular compounds of porphyrin and fullerene molecules in the crystalline state are performed: H2TPPxC60x3 toluene, H2TpivPPxC60, H2T3,5-dimethylPPxC70x4 toluene, and NiT4-methylPPx2C70x2 toluene. The geometry is optimized using the PBE functional and the Grimme DFT-D2 dispersion interaction correction. The electronic structure and absorbance spectra are calculated using the HSE functional. It is shown that the Показано, the H2TPPxC60x3 toluene structure having a sufficiently wide absorbance wavelength range, which results in a photoinduced electron transition from the higher occupied states formed by porphyrin molecules to the lower unoccupied states formed by fullerene molecules, are most promising for the design of photogalvanic elements.



3.
EFFECT OF THE CALCULATION METHOD AND THE BASIS SET ON THE STRUCTURE AND ELECTRIC PROPERTIES OF (4,4) CARBON NANOTUBES WITH DIFFERENT LENGTHS AND OPEN ENDS

E.V. Butyrskaya, S.A. Zapryagaev, L.S. Nechaeva, A.A. Karpushin, E.A. Izmailova
Voronezh State University, Voronezh, Russia
Keywords: квантово-химическое моделирование, углеродные нанотрубки, размерные эффекты, структура углеродных нанотрубок, термодинамические характеристики, электрические свойства, quantum chemical simulation, carbon nanotubes, size effects, structure of carbon nanotubes, thermodynamic characteristics, electric properties

Abstract >>
The structure and electric properties of open carbon nanotube chirality (4,4), consisting of 5-15 segments, are calculated within four quantum chemical models: AM1, PM3, LSDA/3-21G*, and B3LYP/6-31G. Size effects and the effect of the model choice on the geometry, energy, enthalpy and Gibbs energy of the formation (atomization), Mulliken atomic charges, polarizability, and predicted adsorption properties of nanotubes are discussed.



4.
ION MOBILITY AND CONDUCTIVITY IN THE Li(NH3CH2COO)(NO3)

V.Ya. Kavun, A.A. Udovenko, N.V. Makarenko, L.A. Zemnukhova, A.B. Podgorbunskii
Institute of Chemistry, Far East Branch, Russian Academy of Sciences, Vladivostok, Russia
Keywords: нитратоглицинат лития, кристаллическая структура, ЯМР (Li, H) спектроскопия, ионная подвижность, ионная проводимость, lithium nitratoglycinate, crystal structure, NMR spectroscopy, ion mobility, ion conductivity

Abstract >>
Compound (7Li, 1H) NMR and impedance spectroscopy methods are used to study the ion mobility and conductivity in a complex of the composition Li(NH3CH2COO)(NO3) (I), which has a layered crystal structure. The character of ion motions in lithium and proton sublattices with temperature variation is considered; the types of motions and temperature ranges in which they occur are determined. It is found that above 350 K the dominant process in the lithium sublattice of the compound is Li+ ion diffusion. Possible migration paths of lithium ions in the lattice of the compound are analyzed. The conductivity of the compound is found to be 2.4x10-6 S/cm at 393 K.



5.
EPR OF COPPER IONS IN Pb2MoO5 CRYSTALS

V.A. Nadolinnyi, A.A. Ryadun, V.N. Shlegel', N.V. Ivannikova
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: ЭПР спектроскопия, кристаллы PbMoO, примесные ионы меди, EPR spectroscopy, PbMoO crystals, impurity copper ions

Abstract >>
The article presents the results of EPR studies of Pb2MoO5 crystals containing a copper impurity. Based on the analysis of angular dependences of the EPR spectra, it is found that copper ions incorporate into the structure of the Pb2MoO5 crystal in the Cu2+ state and occupy the molybdenum site with the formation of a linear extended Cu(II)-V(O)-Pb(IV) defect along the а axis of the crystal. An oxygen vacancy appears in the structure of the defect to compensate the charge and the lead ion acquires the Pb4+ charge state. According to the structure of this center, one magnetically non-equivalent position with the direction of main values of А and g of A (Cu) zz and gzz tensors parallel to the а axis is observed in the EPR spectra. Moreover, the EPR spectra exhibit an addition hyperfine structure from one lead atom on which the unpaired electron density is 0.061 %. The obtained data on the structure of the defect formed when the copper impurity incorporates into the Pb2MoO5 crystal provided the assumption that the observed light scattering when the light beam is directed perpendicular to the а axis may be due to the cooperative effect of the presence of di- and tetravalent ions substituting for molybdenum in the linear configuration of Pb-O-Mo bonds.



6.
X-RAY PHOTOELECTRON STUDY OF THE EFFECT OF THE COMPOSITION OF THE INITIAL GAS PHASE ON CHANGES IN THE ELECTRONIC STRUCTURE OF HEXAGONAL BORON NITRIDE FILMS OBTAINED BY PECVD FROM BORAZINE

E.A. Ilinchik†, I.S. Merenkov
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: гексагональный нитрид бора, рентгеновская фотоэлектронная спектроскопия, электронное строение, тонкие пленки, PECVD, боразин, наностенки, hexagonal boron nitride, X-ray photoelectron spectroscopy, electronic structure, thin films, borazine, nanowalls

Abstract >>
Hexagonal boron nitride films are synthesized by plasma enhanced chemical vapor deposition (PECVD) from a gas mixture of borazine and ammonia or helium on a Si(100) substrate. X-ray photoelectron spectroscopy is used to study changes in the electronic structure and chemical composition of the films depending on the composition of the initial gas mixture. It is found that the chemical composition of the samples obtained depends on the gas used. The use of helium results in an excess of boron atoms on the film surface, the appearance of B-B bonds, and a decrease in the contribution of B-N bonds in the hexagonal environment. The preparation of h-BN films close to the stoichiometric composition by PECVD methods with the use of borazine is shown to be possible with the addition of ammonia. Based on the literature data, the binding energies in the B 1 s spectra are calculated for different boron environments in the hexagonal lattice.



7.
CHARACTERIZATION AND CRYSTAL STRUCTURE OF A NEW LAYERED CADMIUM DIPHOSPHATE: KCdHP2O7x2H2O

Salah Kouass1, Ahmed Selmi2,3, Hammouda Chebbi4,5, Abderrahmen Guesmi5,6
1Institut National de Recherche et d'Analyse Physico-chimique Sidi-Thabet, 2020 Tunis, Tunisia
2Universite de Gafsa, Sidi Ahmed Zarroug, 2112 Gafsa, Tunisia
3Universite de Carthage, 7021 Zarzouna, Bizerte, Tunisia
4Universite de Tunis, Rue Jawaher Lel Nehru, 1089 Montfleury, Tunis, Tunisia
5Universite de Tunis El Manar, El Manar II, 2092 Tunis, Tunisia
6Al-Baha University, Al Mukhwah, Al Baha Region, Kingdom of Saudi Arabia
Keywords: crystal structure, cadmium diphosphate, bond-valence-sum, FT-IR, Raman

Abstract >>
A new potassium cadmium hydrogen diphosphate dihydrate, KCdHP2O7×2H2O (1), has been synthesized by slow evaporation at room temperature and characterized by FT-IR, Raman, TG-DTA, and single crystal X-ray diffraction. Compound (1) crystallizes in the orthorhombic Pcmn space group with the unit cell parameters a = 6.5814(8) Å, b = 7.9428(9) Å, c = 15.961(6) Å, V = 834.4(3) Å3 and Z = 4. Its structure consists of polyhedral layers parallel to the ab plane where each CdO6 octahedron ( m position) shares four edges with three different diphosphate groups. In the Cd octahedron, two oxygen atoms residing in ( m ) special positions belong to coordinated water molecules. These layers are joint by K+ cations (4 c Wyckoff position) and hydrogen bonds, leading thus to a two-dimensional framework. The structural model is supported by the bond-valence-sum validation tool as calculated valences are close to the formal oxidation numbers.



8.
STRUCTURE OF HYDROGEN FLUORIDE COMPLEXES WITH DIETHYLKETONE IN A HF-Et2CO SOLUTION

E. G. Tarakanova, G. V. Yukhnevich
N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
Keywords: двойная жидкая система, ИК спектроскопия, водородная связь, комплексы фтористого водорода, HF, диэтилкетон, binary liquid system, IR spectroscopy, hydrogen bond, complexes of hydrogen fluoride, diethylketone

Abstract >>
The optimal configurations and the vibrational spectra of heteroassociates (HA) of hydrogen fluoride and diethylketone molecules with 1:1, 2:2, 4:1, and 8:2 compositions are calculated using the density functional theory (B3LYP/6-31++G(d,p)). A comparison of the results of calculations and the known experimental data reveal that the following stable hydrogen-bonded molecular complexes are formed in HF-Et2CO solutions: the C2h-symmetry cyclic heterotetramer (HF)2×(Et2CO)2 and the tricyclic HA (HF)8×(Et2CO)2 formed based on the heterotetramer by the binding of two (HF)3 moieties. It is shown that it is appropriate to decompose the spectral curve into the Gaussian functions or the Lorentzian functions to determine the frequencies and the integrated intensities of broad and overlapped IR bands. The first type of the decomposition enables one to estimate more correctly the values of the band frequencies, and the second type makes it possible to find more correctly the band intensities.



9.
INTERACTION OF A FUNCTIONAL GROUP AND HYDROCARBON RADICALS OF L-ALANINE AND GLYCINE AMINO ACIDS IN AQUEOUS NaCl, KСl, AND UREA SOLUTIONS AT DIFFERENT TEMPERATURES

V.P. Korolev1,2, O.A. Antonova1,2, A.L. Serebryakova1,2
1Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
2Ivanovo State University of Chemical Technology, Ivanovo, Russia
Keywords: калориметрия, теплота растворения, коэффициенты парного и тройного взаимодействия, вклады групп, водные растворы, L-аланин, хлорид натрия, хлорид калия, мочевина, calorimetry, heat of dissolution, pair and triple interaction coefficients, contributions of groups, aqueous solutions, L-alanine, sodium chloride, potassium chloride, urea

Abstract >>
Dissolution heats of L-alanine in aqueous NaCl ( m ≤ 5 mol/kg water) and KCl ( m ≤ 4 mol/kg water) solutions are measured by the calorimetric method at temperatures of 288 K, 298 K, and 313 K. Enthalpic and heat capacity coefficients of the pair and triple interaction of alanine with non-aqueous components are determined. By means of the literature data the contributions of charged COO- groups and hydrocarbon radicals of (СНСН3 of L- alanine and СН2 of glycine) in water mixtures with NaCl, KCl, and urea are found. The effects of the nature of additives and temperature on the interactions of hydrophilic and hydrophobic groups of the amino acids in the mentioned systems are discussed.



10.
CRYSTALLOGENETIC ANALYSIS OF FLUORIDOBORATES AND ANALOGUES WITH THE CATIONIC М7-FRAMEWORK

V.V. Bakakin1, Yu.V. Seretkin2,3
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Sobolev Institute of Geology and Mineralogy, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
3Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: катионные подрешетки, катионные каркасы, темплаты, ортобораты, фторидобораты, cation sublattices, cation frameworks, templates, orthoborates, fluoridoborates

Abstract >>
The organization principles of crystal structures of a series of fluoridoborates with large cations and their topological analogues are considered based on the current cation framework representations. Outer-framework anionic components are differentiated into leading (template) and subordinate with respect to their structure directing function.



11.
CRYSTALLOGRAPHIC ANALYSIS OF SULFIDES RELATED TO BISMUTHINITE Bi2S3

S.V. Borisov, S.A. Magarill, N.V. Pervukhina
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: кристаллографический анализ, сульфиды, псевдотетрагональный катионный каркас, псевдогексагональный анионный каркас, семейство висмутинит BiS-аикинит CuPbBiS, катионные и анионные подрешетки, связь симметрия-состав, crystallographic analysis, sulfides, pseudo-tetragonal cation framework, pseudo-hexagonal anion, bismuthinite BiS-aikinite CuPbBiS family, cation and anion sublattices, symmetry-composition relationship

Abstract >>
The crystallographic analysis of Bi2S3, CuPbBi5S9, CuPbBi3S6, CuPbBiS3 compounds, representing a series with a successive replacement of a part of Bi atoms by Pb+Cu shows that they are characterized by a stable combination of a pseudo-tetragonal cation framework with a pseudo-hexagonal anion one, which is common for all structures, within orthorhombic unit cells with n sizes of 11.2 , 4, and 11.5. The Bi2S3 cation framework is retained for heavy Bi+Pb, and additional light Cu fill the available vacant sites without changing its geometry but varying the crystallographic symmetry within the orthorhombic crystal symmetry and unit cells of n standard blocks (11,2x4x11,5 Å3).



12.
STRUCTURAL FEATURES OF FexTiSe2 MATERIALS WITH A RETROGRADE SOLUBILITY IN THE SOLID STATE

E.G. Shkvarina1,2, A.N. Titov1,2, S.G. Titova3, O.M. Fedorova3
1Mikheev Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
2El'tsin Ural Federal University, Ekaterinburg, Russia
3Institute of Metallurgy, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
Keywords: полнопрофильный рентгенофазовый анализ, ЯГРС, ретроградная растворимость в твердом состоянии, интеркалированный железом диселенид титана, full-profile powder X-ray diffraction analysis, NGRS, retrograde solubility in the solid state, iron intercalated titanium diselenide

Abstract >>
Changes in the crystal structure, which are accompanied by iron intercalation and release in a layered intercalate TiSe2 compound demonstrating retrograde solubility in the complete solid state are considered. Various concentration regions not exceeding, exceeding, and corresponding to the leakage limit of the overlap of titanium orbitals coordinated by iron are analyzed. It is shown that at low temperatures (below 400 С) the behavior of iron in the TiSe2 lattice is governed by a covalent bond of iron with the lattice whereas at high temperatures (above 1000 С) iron becomes an ionic impurity. In the intermediate temperature range, iron atoms are involved in either covalent or ionic bond with the lattice. When the concentration of iron in the form of the ionic impurity increases, an increase in the cell parameter in the direction perpendicular to the layers is accompanied by a compression of the Se-Ti-Se sandwich and an increase in the van der Waals gap. When the covalent bond forms, there is a decrease in the lattice parameter in the direction perpendicular to the layers, which is accompanied by an increase in the width of the Se-Ti-Se sandwich and a decrease in the van der Waals gap.



13.
INORGANIC ARCHITECTURE BASED ON A {[Ca(H2O)]6[P4W6O34]2}12- BUILDING BLOCK: COUNTERCATION EFFECT ON THE LATTICE SYMMETRY

M.A. AlDamen, S.B. Atta, S.F. Haddad
University of Jordan, Amman, Jordan
Keywords: sandwich polyoxometalates, calcium, crystal structure, cation effect, 3D inorganic lattice

Abstract >>
Three new salts of the {[Ca(H2O)]6[P4W6O34]2}12- polyanion, namely (NH4)12{[Ca(H2O)]6××[P4W6O34]2}×24H2O (1), H2[Na(H2O)1.6]10{[Ca(H2O)]6[P4W6O34]2}×10H2O (2), and [Ca(H2O)5]6{[Ca(H2O)]6[P4W6O34]2}×11H2O (3) are prepared. The change in the lattice as a function of the countercation and its coordination, specially calcium, is investigated. Full characterization is made by single crystal X-ray diffraction and also UV-visible spectroscopy, FT-IR, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS).



14.
X-RAY STUDY OF THE MONOCLINIC MODIFICATION [Cu(NH3)4](ReO4)2 IN 100-410 K RANGE

S.A. Gromilov1,2, S.P. Khranenko1, D.A. Piryazev1,2, N.V. Kuratieva1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: медь, перренат, термолиз, рентгенофазовый анализ, рентгеноструктурный анализ, кристаллохимия, copper, perrhenate, thermolysis, powder X-ray diffraction analysis, single crystal X-ray diffraction analysis, crystal chemistry

Abstract >>
The monoclinic modification of complex [Cu(NH3)4](ReO4)2 salt is studied by single crystal X-ray diffraction in the range of 100-410 K. Crystallographic data at 300 K are as follows: a = 10.6123(3) Å, b = 7.5443(2) Å, c = 15.2261(4) Å, b = 108.406(1)°, V = 1156,67(5) Å3, space group Р 21/ n , Z = 4, d x = 3.623 g/cm3. The coordination environment of the Cu atom is a distorted square formed by four nitrogen atoms; Cu-N of 1.997-2.018 Å; supplemented with contacts with two oxygen atoms Cu…О 2.472 Å and 2.598 Å. A comparative crystallochemical analysis with the triclinic modification of [Cu(NH3)4](ReO4)2 known in the literature is performed.



15.
A DINUCLEAR OXYGEN-BRIDGED SCHIFF BASE IRON(III) COMPLEX DERIVED FROM N,N'-bis(4-METHOXY-2-HYDROXYBENZYLIDENE)-2,2-DIMETHYLPROPANE-1,3-DIAMINE

A. Karahan1, R. Kurtaran2, Y. Yahsi3, E. Gungor3, H. Kara3,4
1Suleyman Demirel University, Isparta, Turkey
2Akdeniz University, Alanya, Antalya, Turkey
3Balikesir University, Balikesir, Turkey
4Mugla Sitki Kocman University, Mugla, Turkey
Keywords: Schiff-base ligand, iron(III) complex, X-ray crystal structure analysis, oxo-bridged structure

Abstract >>
The μ-oxo-bridged Fe(III) dimer complex [{Fe(4-MeOL1)}2(m-O)]×HOCH3, (H2-4-MeOL1 = N , N '-bis(4-methoxy-2-hydroxybenzylidene)-2,2-dimethylpropane-1,3-diamine), 1 is synthesized and characterized by single crystal X-ray diffraction. Complex 1 contains a [{Fe(4-MeOL1)}2(μ-O)] dimeric unit with a methanol solvent molecule of crystallization. Each Fe(III) ion has a distorted square-pyramidal coordination geometry. In the basal plane, the Fe(III) atom is coordinated by two N and two O atoms of the Schiff base ligand. The apical position is occupied by a bridging O2- ion, linking another Fe(III) ion in the complex. There are intermolecular C-H⋯O and C-H⋯π interactions among the dinuclear complexes.



16.
ORGANIC-INORGANIC HYBRID PEROVSKITE (C6H5(CH2)2NH3)2CdCl4: SYNTHESIS, STRUCTURAL AND THERMAL PROPERTIES

S. Kassou1, A. Kaiba2, P. Guionneau3, A. Belaaraj1
1Universite Moulay Ismail, B.P. 11201, Zitoune, 50000 Meknes, Maroc
2Prince Sattam bin Abdulaziz University, P.O. Box 83, Al-Kharj11942, Saudi Arabia
3CNRS, Universite Bordeaux, ICMCB, UPR 9048, F-33600 Pessac, France
Keywords: layered perovskite, organic-inorganic hybrid, structural phase transition, single crystal, differential scanning calorimetry (DSC)

Abstract >>
The present research work reports the study on crystal structure, vibrational spectroscopy and thermal analysis of organic-inorganic hybrid compound (C6H5(CH2)2NH3)2CdCl4. Single crystals of bis(phenethylammonium)tetrachlorocadmate (C6H5(CH2)2NH3)2CdCl4 (PEA-Cd) were obtained by diffusion at room temperature. This compound crystallizes in the orthorhombic space group C 2 cb with unit cell parameters a = 7.4444(2) Å, b = 38.8965(3) Å, c = 7.3737(2) Å and Z = 4. Single crystal structure has been solved and refined to R = 0.036 and wR = 0.092. The structure consists of an extended [CdCl4]2- network and two [C6H5(CH2)2NH3]+ cations to form a two-dimensional perovskite system. The infrared (IR) spectrum of the title compound was recorded at room temperature. Differential scanning calorimetry (DSC) was used to investigate the phase transition; this compound exhibits a reversible single solid-solid phase transition.



17.
STRUCTURES, PROPERTIES AND TOPOLOGIES OF TWO LAYERED COMPOUNDS BASED ON 2-CARBOXETHYL(PHENYL)PHOSPHINIC ACID

B. Liu1, Z.-H. Zhang2, L. Xu1,2, H. Jiao2
1Shaanxi University of Sciences and Technology, Xi'an, Shaanxi, P. R. China
2Shaanxi Normal University, Xi'an, Shaanxi, P. R. China
Keywords: crystal structure, fluorescence, 2-carboxyethyl(phenyl)phosphinic acid, TGA, topology

Abstract >>
Hydrothermal syntheses of 2-carboxyethyl(phenyl)phosphinic acid (H2CEPPA) with Bi(NO3)3 and Cd(NO3)2 produce two layered complexes [Bi23-O)(CEPPA)2] n (1) and [Cd(HCEPPA)2] n (2). Compound 1 is comprised of [Bi4(m3-O)2(POO)4(COO)4] SBUs which grow into a double wave-like 2D layer with -CH2CH2- spacers. Compound 2 crystallizes in the orthorhombic noncentrosymmetric space group Pca 21, exhibiting a double lattice-like layer. Through edge-to-face d ⋯π stacking, a 3D supramolecular framework is formed based on 2D lattices. Topological analyses indicate that 1 and 2 have sql (or Shubnikov tetragonal plane net) and kgd (or Shubnikov (3.6.3.6) plane net) topological networks respectively. 1 and 2 are isolated as single crystal pure phases, which is confirmed by powder XRD. TGA shows high thermal stabilities with decomposition temperatures of 1 and 2 being 373 and 303 °C respectively. The fluorescent spectra exhibit fluorescence quenching in 1 and sharp emission at 292 nm in 2, which is assigned to intraligand emission.



18.
CRYSTAL STRUCTURE OF A NEW BINUCLEAR COMPLEX bis(2,4,6,8-TETRAMETHYL-2,4,6,8-TETRAAZABICYCLO(3.3.0)OCTANE-3,7-DIONE-O,O)-TETRAAQUA-hexakis(NITRATO-O,O)-DIEUROPIUM(III)

E.E. Netreba1, E.A. Sarnit1, S.V. Shabanov1, A.A. Velikozhon1, N.V. Somov2
1Taurida Academy of Vernadsky Crimean Federal University, Simferopol, Russia
2Lobachevsky State University, Nizhny Novgorod, Russia
Keywords: бициклические бисмочевины, мебикар, европий(III), структура, десятивершинник, ИК, РСА, bicyclic bisureas, mebicar, europium(III), structure, 10-vertex polyhedron, IR, single crystal XRD

Abstract >>
A centrosymmetric binuclear complex of europium(III) nitrate with bicyclic bisurea (2,4,6,8-tetramethyl-2,4,6,8-tetraazabicyclo(3.3.0)octane-3,7-dione, or mebicar, Mk) [Eu(C8H14N4O2)(H2O)2(NO3)3]2 (I) is synthesized and its atomic structure (CIF file CCDC No. 1451437) is determined. The crystals of I are triclinic: space group P , a = 9.8343(4) Å , b = 10.2544(4) Å, c = 10.9411(4) Å, a= 74.366(3)°, = 67.734(4)°, b= 67.673(4)°, V = 934.32(7) Å3, ρ(calc.) = 2.03398 g/cm3, Z = 1. The europium atom is coordinated by two oxygen atoms of two Mk molecules connected by a symmetry operation, three bidentate nitrate anions, and two water molecules. The coordination polyhedron of the europium atom is a 10-vertex polyhedron, the Eu…Eu distance is 9.7433(6) .



19.
MOLECULAR AND CRYSTAL STRUCTURE OF 1,2-BIS(METHYL-ONN-AZOXY-OXY)ETHANE

Z. G. Aliev, I. N. Zyuzin, S. M. Aldoshin
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia
Keywords: алкокси-NNO-азоксисоединения, алкил-ONN-азокси-оксисоединения, 1,2-бис(метил-ONN-азокси-окси)этан, кристаллическая структура, гош-конформация, alkoxy-NNO-azoxy compounds, alkyl-ONN-azoxy-oxy ​compounds, 1,2-bis(methyl-ONN-azoxy-oxy) ethane, crystal structure, gauche conformation

Abstract >>
The molecular and crystal structure of 1,2-bis(methyl-ONN-azoxy-oxy)ethane is studied. Its molecule has a gauche conformation with respect to the С-С bond with a torsion angle of 71.4°.



20.
CRYSTAL STRUCTURE OF PHENYLHYDRAZINE WITH DIACETYL-SUBSTITUTED KETOL OF A CYCLOHEXANE SERIES

A.M. Maharramov1, A.I. Ismiyev1, M.A. Allahverdiyev1, A.V. Maleev2, K.A. Potekhin2
1Baku State University, Baku, Azerbaijan
2Vladimir State University, Vladimir, Russia
Keywords: конформация циклов, ОІ-кетолы, N-фенилпиразолы, cycle conformation, ОІ-ketols, N-phenylpyrazoles

Abstract >>
The reaction of 2,4-diacetyl-5-hydroxy-5-methyl-3-phenylcyclohexanone-1 with phenylhydrazine is conducted, and the crystal structures of its products, 1-(6-hydroxy-3,6-dimethyl)-2,4-diphenyl-4,5,6,7-tetrahydro-2H-indazol-5-yl)ethane-1-one and 1-(2-hydroxy-2-methyl-6-phenyl-4-(2-phenylhydrazono)-5-(1-(2-henylhydrazono)ethyl)cyclohexyl)ethane-1-one, are determined by single crystal XRD.



21.
SAS_ANALYZER SOFTWARE FOR SMALL ANGLE X-RAY SCATTERING DATA ANALYSIS

S.A. Poluyanov1, F.V. Tuzikov1, Yu.V. Larichev1,2, S.V. Tsybulya1,2
1Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: малоугловое рентгеновское рассеяние, обработка данных, минимизация, наноразмерные системы, small-angle X-ray scattering, data processing, minimization, nanosized systems

Abstract >>
New approaches to the small-angle scattering data analysis for nanosized systems are presented. They are based on the application of optimization methods and a repeated solution of direct problems. Based on the new approaches the program is developed which makes it possible to simulate small-angle X-ray diffraction data, to introduce collimation corrections, and to analyze the disperse composition of samples. Results of the program performance are demonstrated for a series of typical nanosized systems (sols, catalysts) and the program is compared with the available programs for small-angle data processing.



22.
SUPRAMOLECULAR ARCHITECTURE OF CRYSTALS OF PERFLUORINATED 3-ALKYLPHTHALIDES

T.V. Rybalova1,2, Yu.V. Gatilov1,2, Ya.V. Zonov1,2, V.M. Karpov1
1Vorozhtsov Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: 3-гидрокси-перфтор-3-алкилфталиды, рентгеноструктурный анализ, межмолекулярные взаимодействия, квантово-химические расчеты, супрамолекулярная архитектура, полиморфы, 3-hydroxyperfluoro-3-alkylphthalides, single crystal X-ray diffraction study, intermolecular interactions, quantum chemical calculations, supramolecular architecture, polymorphs

Abstract >>
The molecular and crystal structures of perfluoro-3-alkylphthalides (3-hydroxyperfluoro-3-methylphthalide and its hydrate, two polymorps of 3-hydroxyperfluoro-3-ethylphthalide and 3-hydroxyperfluoro-3-isopropylphthalide) are determined by single crystal X-ray diffraction. In the crystals, the supramolecular O-Н…O=C synthon occurs leading, except for the crystallohydrate, to the formation of hydrogen bonded chains (6) (supramolecular 1D motifs). According to the DFT/M06-2X/TZV calculations, the interaction energy of hydrogen bonded molecular pairs increases in this series, which can be explained by the additional C=O…π, O…π and C-F…π interactions.



23.
STRUCTURE AND PHOTOLUMINESCENCE PROPERTIES OF TiO2 NANOPARTICLES SYNTHESIZED FROM A NOVEL LUMINESCENT NANO-TITANIUM COMPLEX

V. Jodaian1, N.S. Langeroodi2, E. Najafi3
1Islamic Azad University, Islamshahr Branch, Iran
2Golestan University, Gorgan, Iran
3Payame Noor University, Tehran, Iran
Keywords: titanium complex, photoluminescence, size effect, TiO, Raman vibration

Abstract >>
A new titanium complex [Ti(Me-Q)2(Cl)2] (1) is prepared by reacting titanium tetrachloride with 2-methyl-8-hydroxyquinoline in a fast and facile process. The complex is fully characterized based on its 1H and 13C NMR, IR, and UV spectra and elemental analysis. The prepared nanostructured compound is synthesized by the sonochemical method. This new nanostructure is characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), IR spectroscopy, and elemental analysis. Thermal stability of single crystalline and nanosize samples of the prepared compound is studied by thermal gravimetric (TG) and differential thermal analysis (DTA). The prepared complexes both bulk and nanosized are utilized as a precursor for the preparation of TiO2 nanoparticles by direct thermal decomposition at 600 °C in air. The morphology and size of TiO2 nanoparticles are determined by SEM, powder XRD, and IR spectroscopy and the results show that the TiO2 nanoparticle size depends on the initial particle size of 1. Photoluminescence (PL) properties of the nanostructured and crystalline bulk prepared complex and their TiO2 nanoparticle cores are investigated.



24.
STRUCTURES OF IV GROUP ELEMENTS AND SOLID PHASES OF WATER

G.G. Malenkov
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russia
Keywords: полиморфизм, лед, углерод, кремний, германий, олово, кристаллические структуры, аморфные тела, клатратные соединения, polymorphism, ice, carbon, silicon, germanium, tin, crystal structures, amorphous bodies, clathrate compounds

Abstract >>
The structures of solid phases of water and IV(b) group elements of the periodic table (carbon, silicon, germanium, and tin) are compared. Both water and mentioned elements are characterized by high polymorphism. All mentioned elements and ice have a modification with a diamond structure. For all substances considered, except tin, modifications with the structure of a hexagonal analogue of diamond (lonsdaleite) have been known. The modification with the β-Sn structure has not been known only for ice and carbon. One of the germanium modifications is isostructural to ice III. Tin has a modification with the α-Fe structure. The same structure is observed for ices VII, VIII, and X. Both water and IVb group elements can form clathrate hydrates with cavities in the form of Allen's polyhedra. In water clathrates these cavities contain noble gas atoms (Ar, Kr, Xe) and various molecules. Clathrates of IVb group elements contain metal atoms as well as noble gas atoms.



25.
ELECTRONIC STRUCTURE OF NON-STOICHIOMETRIC LAYERED LaZnAsO1-Оґ COMPOSITIONS WITH A ZrCuSiAs-LIKE STRUCTURE, AS FOLLOWS FROM THE FLAPW-GGA MODELING

V.V. Bannikov, I.R. Shein
Institute of Solid State Chemistry, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
Keywords: 1111 фазы, нестехиометрия, ab initio моделирование, 1111 phases, non-stoichiometry, ab initio simulation

Abstract >>
Features of the electronic structure of layered LaZnAsO1- δ phases with the ZrCuSiAs structure type at δ = 0.11 and 0.44 are briefly discussed based on the results of ab initio calculations. It is shown that the effect of oxygen vacancies on the electronic structure of non-stoichiometric phases is equivalent to the effect of an electron dopant and the charge compensation occurs inside [La-O] structural blocks due to a change in the population of lanthanum atomic states.



26.
MOLECULAR DYNAMICS STUDY OF DEFECT FORMATION WITHIN THIN GRAPHITE FILMS USING DENSITY FUNCTIONAL TIGHT-BINDING METHOD

I. R. Shein, M. V. Kuznetsov, A. N. Enyashin
Institute of Solid State Chemistry, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
Keywords: графен, графит, точечные дефекты, метод функционала электронной плотности, молекулярная динамика, graphene, graphite, point defects, density functional theory, molecular dynamics

Abstract >>
Point defect formation within graphene and ultra-thin graphite films is considered by means of molecular dynamics simulations in the framework of density functional tight-binding approach. The barrier energy for vacancy formation is estimated and two types of defect formation are revealed.



27.
FREE WATER IN BEAN SEEDS: THE IMBIBITION PROCESS ACCORDING TO THE MAGNETIC RESONANCE MICROTOMOGRAPHY DATA

I.S. Vinogradova1, O.V. Falaleev2
1Siberian State Technological University, Krasnoyarsk, Russia
2Kirensky Institute of Physics, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russia
Keywords: Н магнитно-резонансная микротомография , семена фасоли, набухание семян, распределение воды, Н magnetic resonance microtomography , Carolina beans, bean swelling. water distribution

Abstract >>
The results of the 1Н magnetic resonance microtomography study of large Carolina beans during their swelling in water are presented. The studies are performed using two-dimensional longitudinal tomographic sections. Channels through which water incomes to a swelling beam are determined and the heterogeneity of its distribution inside the bean is shown.



28.
CRYSTAL STRUCTURE OF NOVEL LAYERED IRON ARSENATE-OXALATE (NH4)3K3[Fe2(HAsO4)2(C2O4)4]x2H2O

N. Ouerfelli1,2, H. Chebbi1,3, Zid M. Faouzi1
1Universite de Tunis El Manar, El Manar II, Tunis, Tunisia
2Universite de Tunis Carthage, Bizerte, Tunisia
3Universite de Monastir, Monastir, Tunisia
Keywords: iron arsenate-oxalate, synthesis, single crystal X-ray diffraction, crystal structure

Abstract >>
A new open-framework structure of iron arsenate-oxalate (NH4)3K3[Fe2(HAsO4)2(C2O4)4]x2H2O (I) is synthesized by slow evaporation and structurally characterized by single crystal X-ray diffraction methods. It crystallizes in the triclinic space group P (No . 2), with a = 10.154(4) Å, b = 10.430(4) Å, c = 15.085(7) Å, a = 96.81(3)°, b = 105.04(43)°, g = 93.93(3)°, V = 1523.7(11) Å3 and Z = 2. Its crystal structure consists of two crystallographically independent bishydrogenarsenato tetraoxalato diiron(III) anions, both located on centres of inversion, while the potassium and ammonium cations and water molecules are located in general positions.These moieties are connected through N - H…O and O - H…O hydrogen bonds to form infinity of layers parallel to the (101) plane, thus leading to a two-dimensional open framework.



29.
CRYSTAL STRUCTURE OF THE COMPLEX OF COPPER(II) WITH 3-(2-HYDROXY-3-SULFO-5-NITROPHENYLAZO)-PENTADIONE-2,4

A.M. Maharramov, R.A. Alieva, G.G. Nazarova, F.N. Bakhmanova, R.K. Askerov, F.M. Chyragov
Baku State University, Baku, Azerbaijan
Keywords: комплекс, медь, монокристалл, ОІ-дикетоны, complex, copper, single crystal, ОІ-diketones

Abstract >>
A new complex of copper (II) with 3-(2-hydroxy-3-sulfo-5-nitrophenylazo)-pentadione-2,4 (HL) is synthesized and analyzed by single crystal XRD. The crystals are monoclinic: a = 7.7563(4) Å, b = 24.0157(12) Å, c = 24.6353(13) Å, b = 91.9490(10) °, V = 4586.2(4) Å3, space group P 21/ c , Z = 2, ρcalc = 1.713 g/cm3, R = 0.0695. The copper atom environment is formed by three oxygen atoms, the nitrogen atom of the tetradentate ligand, and the oxygen atom of a water molecule.



30.
CRYSTAL STRUCTURE OF THE cis-[PdCl2(CNMes)2] COMPLEX

M.A. Kinzhalov, A.A. Zolotarev, V.P. Boyarskii
St. Petersburg State University, St. Petersburg, Russia
Keywords: комплексы палладия, изоцианиды, palladium complexes, isocyanides

Abstract >>
The interaction between PdCl2(CH3CN)2 and 2,4,6-Me3C6H2NC (MesNC) proceeds with the substitution of acetonitrile ligands and leads to the synthesis of a cis -[PdCl2(MesNC)2] complex. The structure of this compound is determined by single crystal X-ray diffraction. The complex has a slightly distorted square-planar structure of the metal center with two cis -positioned isocyanide ligands. The triple bonds in both CN isocyanide fragments have lengths similar to the lengths of the corresponding bonds in other isocyanide complexes. In the structure, the cis -[PdCl2(MesNC)2] complexes are bound by weak С-H⋯Cl hydrogen bonds and p-stacking interactions.



31.
CRYSTAL STRUCTURE INVESTIGATION OF RUTHENIUM(III) TRIS-DIPIVALOYLMETHANATE

S.V. Sysoev1,2, D.Yu. Naumov1,3, N.V. Kuratieva1,3, K.V. Zherikova1, S.A. Gromilov1,3, N.B. Morozova1, T.M. Kuzin1, N.V. Gelfond1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University of Architecture and Civil Engineering, Novosibirsk, Russia
3Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: рутений, дипивалоилметан, рентгеноструктурный анализ, кристаллохимия, ruthenium, dipivaloylmethane, single crystal X-ray diffraction analysis, crystal chemistry

Abstract >>
The structure of ruthenium(III) dipivaloylmethanate is determined by single crystal X-ray diffraction at a temperature of 150 K. The crystallographic data for C33H57O6Ru are as follows: a = 9.6119(11) Å, b = 17.4603(19) Å, c = 21.519(2) Å, β = 95.187(2)°, space group C2/c, V = 3596.7(7) Å3, Z = 4, dcalc = 1.202 g/cm3, R = 0.0642. The structure is molecular, the metal atom coordinates six oxygen atoms of three β-diketone ligands. The Ru-O distances are in the range of 1.99 Å to 2.03 Å. The complexes have a distorted single-layer hexagonal packing with the Ru…Ru distances being 9.84 Å within the layer, and 10.93 Å between the layers.



32.
CRYSTAL STRUCTURE OF TWO HOMOCHIRAL METAL-ORGANIC POLYMERS BASED ON S-3,3-DIMETHYLLACTIC ACID

M.S. Zavakhina, D.G. Samsonenko, V.P. Fedin
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: кристаллическая структура, координационные полимеры, хиральные комплексы, супрамолекулярные взаимодействия, crystal structure, coordination polymers, chiral complexes, supramolecular interactions

Abstract >>
By heating of an aqueous solution of zinc(II) or cobalt(II) acetates, 4,4-bipyridyl (bpy), and S -3,3-dimethyl hydroxypropionic acid (H2dml) two homochiral coordination polymers [Zn(H2O)(bpy)(Hdml)](CH3COO)2H2O (1) and [Co(H2O)(bpy)(Hdml)2] (2) are obtained. The crystal structure is determined by single crystal X-ray diffraction. Compound 1 has a layered structure and compound 2 has a chain structure.



33.
STRUCTURAL CHARACTERIZATION OF A NEW COBALT(II) COMPLEX OF 1-BENZYL-5-METHYL-1H-IMIDAZOLE

M. Bouchouit1, A. Bouraiou1, S. Bouacida1,2, A. Belfaitah1, H. Merazig1
1Universite des freres Mentouri, Constantine, 25000, Algerie
2Universite Oum El Bouaghi, 04000 Oum El Bouaghi, Algerie
Keywords: X-ray crystallographic analysis, imidazole, cobalt complex, crystal structure

Abstract >>
The preparation of a cobalt(II) chloride complex with a N-donor ligand 1-benzyl-5-methyl-1 H -imidazole of formula [CoCl2(1-benzyl-5-methyl-1 H -imidazole)2] is described. The isolated complex was characterized by UV, IR spectroscopy and crystallographic studies. Single crystal X-ray diffraction analysis of the complex reveals its monomeric tetra-coordinated nature. The coordination polyhedron around the cobalt center can be described as a quasi-regular tetrahedron. The Co-N distances for this compound are 2.0111(17) Å and 2.0118(17) Å, while the Co-Cl distances are 2.2582(7) Å and 2.2549(7) Å. The crystal packing can be described as layers parallel to (101) plane alternating along the b axis, and it is stabilized by p-p stacking between the imidazole and phenyl rings. The shortest centroid-centroid distance is 3.6002(14) Å.



34.
SUBSTITUENT GROUP EFFECTS ON THE SELF-ASSEMBLY OF OXOVANADIUM(V) COMPLEXES WITH HYDRAZONE LIGANDS BEARING BENZOIC ACID (1-METHYL-3-OXOBUTYLIDENE)HYDRAZIDE BACKBONES

Y.-M. Cui1, D. Yang1, W. Guo2, Q. Wang1, P. Zhang1
1Wuhan Textile University, Wuhan 430073, P. R. China
2Chinese Sturgeon Institute, China Three Gorges Corporation, Yichang 443100, P. R. China
Keywords: hydrazone ligands, oxovanadium(V) complex, self-assembly, substituent effects, crystal structure

Abstract >>
An oxo-bridged dinuclear oxovanadium(V) complex, [V2O2(m-O)(L1)2] (1) [H2L1 = 3-nitrobenzoic acid (1-methyl-3-oxobutylidene)hydrazide], and a mononuclear oxovanadium(V) complex, [VO(OMe)(L2)] (2) [H2L2 = 3-hydroxynaphthalene-2-carboxylic acid (1-methyl-3-oxobutylidene)hydrazide], were prepared by the reactions of [VO(acac)2] with H2L1 and H2L2, respectively, in methanol. Both complexes were characterized by elemental analysis, IR spectra, and single crystal X-ray crystallography. The crystal of 1 crystallizes in the monoclinic space group P 2/ n , with a = 13.116(3), b = 7.597(2), c = 13.927(2) Å, b = 104.851(2)°, V = 1341.4(5) Å3, Z = 2. The crystal of 2 crystallizes in the triclinic space group P , with a = 7.897(2), b = 9.690(2), c = 11.576(3) Å, a = 86.405(2)°, b = 70.597(2)°, g = 85.991(2)°, V = 832.7(3) Å3, Z = 2. The V atoms in the complexes have square pyramidal environment. The substituent groups attached to the aromatic rings can influence the self-assembly of the complexes.



35.
CRYSTAL STRUCTURE OF DI-Ој-AMIDO-bis[DIAMMINEPLATINUM(II)] NITRATE

Q.-S. Ye1, M.-J. Xie2, X.-N. Li3, W.-P. Liu1, J. Yu1, Q.-W. Chang1, J. Jiang1, C.-X. Yan1, J. Li1
1Kunming Institute of Precious Metals, Kunming 650106, P. R. China
2Yunnan University, Kunming 650031, P. R. China
3Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650201, P. R. China
Keywords: platinum, amide, ammine, crystal structure, synthesis

Abstract >>
Di-m-amido-bis[diammineplatinum(II)] nitrate (1) was synthesized as a byproduct during preparation of tetraammineplatinum(II) nitrate. One possible pathway to produce 1 is that [(H3N)2Pt(m-OH)2Pt(NH3)2](NO3)2, a well-known complex forming on treatment of cis -Pt(NH3)2I2 with AgNO3, reacts with aqueous ammonia. The other possible pathway involves deprotonation of [Pt(NH3)4](NO3)2 to form monomeric Pt(NH3)3(NH2)NO3 followed by elimination of NH3. Crystals of 1 (from water) are monoclinic ( C 2/ c ) with a = 16.834(2) Å, b = 10.573(1) Å, c = 7.415(1) Å, b = 114.846(1)°, and Z = 4. The cationic portion consists of two symmetrical square-planar Pt centers with the inversion center at the midpoint of the Pt(1)⋯Pt(1A) vector. The Pt(II) ion is coordinated by four N atoms from two ammonia molecules and two bridging amido groups affording a slightly distorted square. The molecules are stacked in such a way that the planes of coordination squares turn out to be parallel to each other with a distance of 3.501 Å. Intermolecular Pt-H interaction between the m-NH2 hydrogens and the platinum(II) centers of the adjacent molecule are observed.