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Journal of Structural Chemistry

2014 year, number 5

1.
MEASURES OF UNPAIRED ELECTRONS FOR LARGE CONJUGATED SYSTEMS

A. V. Luzanov
Institute for Single Crystals, National academy of Sciences of Ukraine, Kharkov, Ukraine
Keywords: electron correlation, number of effectively unpaired electrons, π shell, polycyclic aromatic hydrocarbons, megamolecules, graphene, nanopores

Abstract >>
It is shown that the numerical measure of effectively unpaired electrons Neff, proposed by Head-Gordon in 2003, is a particle-hole index: Neff is reduced to the average occupation of virtual particle-hole pairs. Specific p calculations of the Neff index provide a reasonable interpretation of the radicaloid character of the singlet ground state in complex conjugated systems. The results of the accurate π model (based on the total configuration interaction) and approximate approaches are compared. The coupled cluster method and various Hartree-Fock schemes (UHF and Löwdin EHF scheme) demonstrate an acceptable quantitative description of unpairing effects, UHF being favorable in simplicity of obtaining the measure of unpairing in megamolecules, such as graphene structures. The application of the known Yamaguchi index results in a rougher representation of the radical character of a system.
																								



2.
ELECTRONIC STRUCTURE AND RELATIVE RADIATION STABILITY OF ORTHOPHOSPHATES LnPO4 (Ln = Ce, Nd, Sm)

N. S. Vinogradova1, Yu. V. Shchapova1, S. L. Votyakov1, M. V. Ryzhkov2, A. L. Ivanovskii2
1Zavaritsky Institute of Geology and Geochemistry, Russian Academy of Sciences, Ekaterinburg, Russia
2Institute of Solid State Chemistry, Russian Academy of Sciences, Ekaterinburg, Russia
Keywords: orthophosphates LnPO4(Ln = Ce, Nd, and Sm), ab initio calculations, electronic structure, chemical bond, radiation stability

Abstract >>
The features of the electronic structure and chemical bond in orthophosphates LnPO4 (Ln = Ce, Nd, and Sm) with the monazite structure are studied by the ab initio discrete variation method within the cluster model. The relative radiation stability of these phases is discussed with the use of the calculated parameters of the electronic spectrum, bond population values, and effective atomic charges.
																								



3.
APPLICATION OF DISCRETE-CONTINUUM SOLVATION MODEL IN A QUANTUM CHEMICAL STUDY OF TECHNETIUM(I) PENTACARBONYL BROMIDE DECARBONYLATION

D. A. Mal`tsev, V. I. Baranovskii
Institute of Chemistry, St. Petersburg, Russia
Keywords: technetium pentacarbonyl bromide, variational theory of reaction rates, quantum chemical calculation, density functional method

Abstract >>
Decarbonylation thermodynamics and kinetics of technetium pentacarbonyl bromide are studied by scanning the reaction pathway and by calculating the kinetic parameters within the variational transition state theory. Calculations are performed in the gas phase and with taking into account a solvent by two methods: continual (PCM) and discrete-continual with direct quantum chemical consideration of the nearest solvate shell. Carbon tetrachloride and water are used as the solvents.
																								



4.
STRUCTURE OF PORPHYRIN H-ASSOCIATES, INVERTED PORPHYRINOIDS, AND CORROLES WITH N,N-DIMETHYLFORMAMIDE

D. B. Berezin1, M. A. Krest'yaninov2
1Ivanovo State University of Chemical Technology, Ivanovo, Russia
2Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: porphyrin, porphyrinoid, corrole, inverted porphyrin isomer, N,N-dimethylformamide, -associate, intramolecular hydrogen bond, chemical activity of the NH bond, geometry optimization, NBO analysis

Abstract >>
By means of quantum-chemical calculations (DFT B3LYP, CC-pVDZ basis set) the previously proposed structure and interaction energy of the components of H-associates of meso -tetraphenylporphyrin and its analogues (comp. I-III) with N,N-dimethylformamide (DMF) of the 1:1 composition is confirmed theoretically for the first time. In the ability to form H-associates involving NH bonds of intramolecular coordination centers (CCs) the macrocycles can be ordered as: IIII b < III a < II. Tautomer III b is shown to form an -associate involving an outer-cyclic 2NH proton, and a macrocycle of corrole II has a strong intramolecular H bond in CC. One of the factors determining the NH activity of macrocycles is the degree of a deviation of the intracyclic NH protons from the plane of the molecule in its non-associated form.
																								



5.
THEORETICAL INVESTIGATION OF THE HEAT OF FORMATION AND DETONATION PERFORMANCE ON 1,1,3,5,5-PENTANITRO-1,5-BIS(DIFLUORAMINO)-3-AZAPENTANE SUBSTITUTED

F. Aghabozorgi, M. Hamadanian
University of Kashan, Kashan, I.R. Iran
Keywords: density functional calculations, heat of formation, heat of explosion

Abstract >>
The density functional theory (DFT) calculation is performed on 1,1,3,5,5-pentanitro-1,5-bis(difluoramino)-3-azapentane substituted. The heat of formation (HOF) is predicted by B3LYP and B3P86 methods with the 6-311G** and 6-311++G** basis sets via isodesmic reactions. With NF2 and ONO2 substitution for NO2, HOFs clearly decrease. Furthermore, we designed a detonation reaction for each compound and computed ΔH298, the heat of explosion (Q), and ΔG298 for each reaction. The general trend is that Q increases as ONO2 and NO2 groups are replaced by the NF2 groups.
																								



6.
INVESTIGATION OF SOLVENT EFFECTS ON THE STABILITY AND 15N NMR SHIELDING OF HALLUCINOGENIC HARMINE USING THE PCM MODEL AND NBO INTERPRETATION

A. Tahan1, N. Ahmadinejad2
1Islamic Azad University, Semnan, Iran
2Young Researchers and Elite Club, Tehran, Iran
Keywords: harmine, polarized continuum model (PCM), NMR, NBO interpretation

Abstract >>
Density functional theory (DFT) and Tomasi's polarized continuum model (PCM) are applied for the investigation of the solvent structure and its dielectric constant effects on the relative stability and nuclear magnetic resonance (NMR) tensors of hallucinogenic harmine. All of the used computational methods indicate that the structural stability in protic polar solvents is higher than that in aprotic polar and nonpolar solvents, and the most stable structure was observed in methanol. Also, the natural bond orbital (NBO) interpretation demonstrates that with an increase in the solvent dielectric constant the resonance energy for LP(N9) → σ* and π* interactions of the strutural pyrrole ring increases while the LP(N9) occupancy decreases, and the highest resonance energy and the lowest occupancy are observed in water and methanol. On the other hand, NMR calculations show that there are the lowest values of Δσdir in water and methanol media for both nitrogen nuclei of the harmine structure.
																								



7.
VIBRATIONAL ANALYSIS OF [4-[(E)-PHENYLAZO]PHENYL]ETHANOL BASED ON THE COMPARISON BETWEEN THE EXPERIMENTAL AND DFT CALCULATED RAMAN SPECTRA

B. Minisini1, G. Messager1, I. Piyanzina1,2, N. Delorme3, J.-F. Bardeau3
1Institut Supérieur des Matériaux et Mécaniques Avancés du Mans, UNAM, Le Mans, France
2Insitute of Physics, Kazan Federal University, Kazan, Russia
3Institut de Recherche en Ingénierie Moléculaire et Matériaux Fonctionnels, FR2575, Université du Maine, France
Keywords: azo dye, DFT calculation, Raman spectra

Abstract >>
In this work we assessed the performance of the density functional theory (DFT) approach through a comparison study with the experimental Raman spectrum obtained for [4-[(E)-phenylazo]phenyl]ethanol (ABOH) in the wavenumber range 900–1800 cm-1. The assignment of the ten most active vibrational modes is achieved using the hybrid B3LYP method with the 6311++G(2d,2p) basis set. Two molecules of reference [N-ethyl-4-[(E)-(4-nitrophenyl)azo]anilino]ethanol (Disperse Red 1, DR1) and 4-[(E)-(4-nitrophenyl)azo]aniline (Disperse Orange 3, DO3) are also investigated in order to consider this method in the calculation of the Raman intensities. The experimental Raman spectrum of DR1 is compared with those of the three stable configurations obtained at the B3LYP/6311++G(2d,2p) level.
																								



8.
X-RAY AND AUGER MICROPROBE STUDIES OF VANADIUM-DOPED LAYERED CHROMIUM-COPPER DISULFIDE CRYSTALS

V. V. Sokolov1, E. V. Korotaev1, N. N. Peregudova1, B. M. Kuchumov1, P. A. Prozorov1, M. V. Topyakova2, L. N. Mazalov1,2,3, Yu. P. Dikov4, M. I. Buleev4, A. Yu. Pichugin1, I. Yu. Filatova1, A. S. Berdinskii2, A. A. Velichko2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State Technical University, Novosibirsk, Russia
3Novosibirsk State University, Novosibirsk, Russia
4Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences, Moscow, Russia
Keywords: layered chromium-copper disulfides, crystals, Auger microprobe studies, SEM, EDX analysis, powder X-ray analysis, inclusions

Abstract >>
In the work, X-ray and Auger microprobe studies of the surface of crystals prepared from powder samples of CuCr1-xVxS2 disulfides (x = 0÷0.11) by crystallization from melt in the sulfur vapor atmosphere. Sample slabs cut from ingots include crystalline layered blocks with different orientation of copper-containing extended linear inclusions separated by disulfide matrix layers. The results of the microprobe analysis of regions with copper-containing inclusions and the regions adjacent to them are presented.
																								



9.
H2O–NH4Cl SYSTEM: IS THERE A THERMODYNAMIC RESPONSE TO THE NUCLEATION POINT?

V. P. Korolev
G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: thermodynamics, aqueous solution, ammonium chloride

Abstract >>
According to literature data (J.Phys.Chem.A, 115, 3393–3460 (2011)), NH4Cl concentrations in nanoobjects such as aerosol droplets can be as high as 28m, which corresponds to a 60 % solution (nucleation concentration). At this concentration, the heat of dissolution of the salt is shown to be temperature independent (the heat capacity of dissolution is zero). This means that the entropy of dissolution is also temperature independent. Relative partial enthalpies are determined for the components of the H2ONH4Cl system over the entire range of compositions at 248373 K. The excess enthalpy of the 60 % solution has extreme values of 810 J/mol, 261 J/mol,184 J/mol, and553 J/mol at 273 K, 298 K, 323 K, and 348 K, respectively. At 312 K, » 0. At 298 K, the excess heat capacity and volume show negative nonidealities with a minimum at 60 % for CPE (19.7 J/(mol×K)) and 57% for VE (0.44 cm3/mol). The composition dependence of the specific heat capacity (in relation to a unit of weight) has a minimum at an equimolar salt:water ratio.
																								



10.
CRYSTAL FORMATION FEATURES IN A SERIES OF CHALCOGENIDE STRUCTURES WITH MONOVALENT Tl. ORDERED PACKING EFFECT IN Tl COORDINATION

S. V. Borisov, S. A. Magarill, N. V. Pervukhina
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: crystallographic analysis, cationic and anionic sublattices, Tl-chalcogenides AgTlTe, vrbaite Hg3Tl4As8Sb2S20, gabrielite Tl2AgCu2As3S7, ordered packing effect in coordination, Tl+ coordination

Abstract >>
In order to determine the crystal- forming factors and reasons for irregular coordination of Tl+ cations the crystallographic analysis of the structure of AgTlTe (I), minerals vrbaite Hg3Tl4As8Sb2S20 (II) and gabrielite Tl2AgCu2As3S7 (III) is performed. For I and II the skeleton translational sublattices of all atoms in the structure with the determining contribution of Tl + and anions are found; for II and III the cationic and anionic along with Tl+ sublattices, which form the structure, are found. The incorporation of cations into the Tl+ coordination environment is classified as a consequence of the structure-forming ordering of Tl cations and anions (S, Te) in one matrix, i.e. as the effect of their ordered packing.
																								



11.
CRYSTAL STRUCTURES OF TWO BARIUM 2–THIOBARBITURATE COMPLEXES

N. N. Golovnev1, M. S. Molokeev2
1Siberian Federal University, Krasnoyarsk, Russia
ngolovnev@sfu-kras.ru
2Kirensky Institute of Physics, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russia
Keywords: crystal structure, barium thiobarbiturate, hydrogen bonds, p-p interaction

Abstract >>
The crystal structures of [Ba(H2O)23–HTBA)2]n (I) and [Ba(μ2H2O)(H2O)24HTBA)(HTBA)]n ×2nH2O (II), where H2TBA is 2thiobarbituric acid C4H4N2O2S, are determined. Crystallographic data are as follows: for I, a = 6.8730(1) Å, b = 16.6640(2) Å, c = 11.8504(2) Å, V = 1357.24(4) Å3, space group Pnma, Z = 4; for II, a = 9.134(1) Å, b = 9.853(1) Å, c = 10.020(1) Å, a = 103.674(2)°, b = 99.491(2), g = 101.683(2), V = 836.3(2) Å3, space group P1, Z = 2. In I, the Ba2+ ion coordinates 6μ3HTBA ions and two terminal water molecules with the formation of a distorted square antiprism. The antiprisms are linked with each other into infinite chains by the edges of S atoms. In II, the Ba2+ ion coordinates four water molecules and 5 HTBA ions forming a three-cap trigonal prism. Two BaO8S prisms have four common vertices of O atoms from two m2H2O and two μ4HTBA; they are organized into layers with other pairs. The structures are stabilized by intermolecular hydrogen bonds and the ppinteraction of HTBA ions.
																								



12.
CRYSTAL STRUCTURE OF DOUBLE SODIUM–COPPER(II) PARATUNGSTATE B: Na2Cu3(CuOH)2[W12O40(OH)2]·32H2O

S. V. Radio1, N. A. Melnik1, E. S. Ivantsova1, V. N. Baumer2,3
1Donetsk National University, Donetsk, Ukraine
2Institute for Single Crystals, National Academy of Sciences of Ukraine, Kharkov, Ukraine
3Karazin Kharkov National University, Kharkov, Ukraine
Keywords: paratungstate B anion, isopolytungstate, crystal structure, FTIR spectroscopy, single crystal X-ray diffraction study

Abstract >>
From the solution of the Na2WO4–HNO3Cu(NO3)2H2O system acidified to Z = n(H+)/n(WO42) = 1.17, the light blue crystals of sodium-copper(II) paratungstate B Na2Cu3(CuOH)2[W12O40(OH)2]×32H2O are isolated. Using FTIR spectroscopy, isopoly anion is shown to belong to the structure type of paratungstate B. By single crystal X-ray diffraction analysis, the structure of Na2Cu3(CuOH)2[W12O40(OH)2]×32H2O is solved: triclinic, space group P-1, a = 10.6836(4) Å, b = 12.9066(6) Å, c = 13.6475(5) Å, α = 73.561(4)°, β = 75.685(3), γ = 67.666(4), V = 1648.68(12) Å3 at T = 293 K, Z = 1, dcalc = 3.882 g/cm3. The paratungstate B anion in the structure is surrounded by two centrosymmetric pairs of octahedra {Na(μH2O)2(H2O)3O} and {Cu(4)(μOH)2(H2O)3O} and six CuO6 octahedra forming a three-dimensional structure, in the voids of which uncoordinated H2O molecules are located.
																								



13.
STRUCTURE OF DIETHYLENETRIAMMONIUM TETRABROMOAURATES(III)

E. V. Makotchenko1,2, I. A. Baidina1, I. V. Korol'kov1
1Nikolaev Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberian Branch, Novosibirsk, Russia
2Novosibirsk state university, Novosibirsk, Russia
Keywords: gold, diethylenetriamine, complexes, single crystal X-ray diffraction study

Abstract >>
In HAuBr4 interaction with diethylenetriamine in HBr, new complexes (DienH3)2[AuBr4]3Br3×4H2O (I) and (DienH3)[AuBr4]3×H2O (II) (where DienH33+ is protonated diethylenetriamine) are obtained, which are characterized by elemental analysis, single crystal X-ray diffraction, thermogravimetry, and IR spectroscopy. For I, the crystals are triclinic, crystallize in the space group –1, a = 7.9717(3) Å, b = 11.0178(4) Å, c = 12.6765(5) Å, α = 75.960(1)°, β = 75.031(1), γ = 75.681(1), V = 1023.02(7) Å3, Z = 2. For II, the crystals are orthorhombic, crystallize in the space group Pnma, unit cell parameters are as follows: a = 4.2981(8) Å, b = 15.394(3) Å, c = 13.402(3) Å, V = 886.7(3) Å3, Z = 4.
																								



14.
CRYSTAL STRUCTURES OF [Fe(m-NO2phtpy)2](ClO4)2 AND [Fe(m-Clphtpy)2](ClO4)2 (m-NO2phtpy = 4'-(3-nitrophenyl)-2,2':6',2"-terpyridine and m-Clphtpy = 4'-(3-chlorophenyl)-2,2':6',2"-terpyridine)

W.-W. Fu1,2, F.-X. Zhang1,2, D.-Z. Kuang1,2
1General Colleges and Universities in Hunan Province, Hunan Province, P. R. China
2Hengyang Normal University, Hengyang, P. R. China
Keywords: iron(II) compound, 4'-(3-nitrophenyl)-2,2':6',2"-terpyridine, 4'-(3-chlorophenyl)-2,2':6',2"-terpyridine, crystal structure

Abstract >>
Two iron compounds [Fe(m-NO2phtpy)2](ClO4)2 1 and [Fe(m-Clphtpy)2](ClO4)2 2 are synthesized and their structures are determined by single crystal X-ray diffraction. Crystal data for 1 are: orthorhombic, space group Pcca, a = 25.471(4) Å, b = 10.8182(18) Å, c = 14.682(2) Å, and Z = 4. Crystal data for 2 are: orthorhombic, space group Pnna, a = 14.521(2) Å, b = 23.980(4) Å, c = 23.142(4) Å, and Z = 8. The iron atoms are coordinated by six N atoms from two terpyridines in both compounds. These two compounds are all linked by hydrogen bonds with C as donor and O as acceptor into a 3D network for 1 and a 2D network for 2. If viewed along the c direction in 1 and the a direction in 2, both compounds show the ordered figure with terpyridine overlapped as a square and the phenyl rings overlapped as a rectangle or a square.
																								



15.
SYNTHESIS, SUPRAMOLECULAR SELF-ORGANIZATION, AND THERMAL BEHAVIOR OF THE HETEROPOLYNUCLEAR COMPLEX ([H3O][Au{S2CN(CH2)6}2][Au2{S2CN(CH2)6}4][ZnCl4]2)n

O. V. Loseva1, T. A. Rodina2, A. I. Smolentsev3, A. V. Ivanov1
1Institute of Geology and Nature Management, Far East Branch, Russian Academy of Sciences, Blagoveshchensk, Russia
2Amur State University, Blagoveshchensk, Russia
3Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: zinc dialkyldithiocarbamates with chemisorption properties, forms of gold binding from solutions, heteropolynuclear gold(III)-zinc complexes, crystal and supramolecular structure, X-ray crystallography, 13C MAS NMR, simultaneous thermal analysis

Abstract >>
The interaction of binuclear zinc cyclo-hexamethylenedithiocarbamate [Zn2{S2CN(CH2)6}4] with [AuCl4]- anions in the 2M HCl medium is studied. The result of a heterogeneous reaction involving the chemisorption binding of gold(III) from a solution and partial ion exchange, was the formation of a heteropolynuclear gold(III)-zinc complex as an individual form of gold(III) binding. The crystal and molecular structure of the polymeric complex of the composition ([H3O][Au{S2CN(CH2)6}2][Au2{S2CN(CH2)6} 4][ZnCl4]2)n (I) is determined by single crystal X-ray diffraction. The structure of the complex contains three isomeric complex [Au{S2CN(CH2)6}2]+ cations: centrosymmetric A with the Au(1) atom and two non-centrosymmetric B with Au(2) and C with Au(3). Due to the pairs of non-symmetric secondary Au⋯S interactions of the non-valence type, the non-centrosymmetric cations form a binuclear [Au2{S2CN(CH2)6}4]2+ cation of the BC type. The subsequent structural self-organization of the complex at the supramolecular level also proceeds due to Au⋯S interactions between the binuclear BC and mononuclear A cations, as a result of which zigzag polymeric chains (⋯ [ BC ]⋯ A ⋯) n are formed. The hydronium ion participates in the pairwise binding of [ZnCl4]2- anions by Cl⋯O hydrogen bonds. The multistage process of the thermal destruction of I includes the dehydration of the complex, thermolysis of the dithiocarbamate moiety and [ZnCl4]2- (with releasing metallic gold, ZnCl2, and partial formation of ZnS). The final products of thermal transformations are metallic gold and ZnS.
																								



16.
RELAXIVITY MEASUREMENT OF PORPHYRIN-BASED MAGNETIC RESONANCE IMAGING (MRI) CONTRAST AGENTS

Kh. Haroon-Ur-Rashid1, M.N. Umar2, K. Khan3, M.N. Anjum4, M. Yaseen1
1University of Peshawar, Peshawar, Pakistan
2University of Malakand, Chakdara, Pakistan
3Islamia College University, Peshawar, Pakistan
4Government College University, Faisalabad, Pakistan
Keywords: contrast agent, porphyrin, relaxivity, gadolinium, ligand

Abstract >>
Magnetic Resonance Imaging (MRI) has become a prominent imaging technique in medicine. MRI contrast agents are used to increase the sensitivity of this technique. Recently, a new method for cancer treatment with a less side effect called photodynamic therapy (PDT) has been introduced. In this method cancer tissues are selectively destroyed without injuring the surrounding healthy cells. However, for the successful use of this method, the selection of an appropriate photosensitizer is important. Hence, diagnosis-treat union of MRI and PDT will be significantly promoted if a new family of bi-functional agents is found, which would combine the effects of a contrast agent in MRI and of a photosensitizer in PDT. It will bring great improvement to the cancer diagnosis and treatment. Porphyrins have proved to be useful photosensitizing agents in PDT due to their promising photophysical efficiency and a less side effect. This work briefly describes the research development of porphyrins as a photosensitizer applied in PDT, and also highlights the recent progress in the research on bi-functional agents of MRI-PDT. Diethylenetriamine pentaacetic acid (DTPA) units are incorporated at a meso-position of the porphyrin ring to synthesize new bi-functional agents of MRI-PDT with sufficient water solubility and high relaxation potency. Gd3+ complexes are prepared by the reaction of the high molecular weight porphyrin-based ligand with GdCl3×6H2O. The longitudinal relaxivity measurement indicates 154 % and 251 % enhancement compared to that of the widely used MRI contrast agent Gd–DTPA. These results indicate that the two complexes could possibly be used as bi-functional agents of MRIPDT.
																								



17.
ION MOBILITY AND PHASE TRANSITIONS IN THE COMPOUNDS K0,65Rb0,35SbF4 AND (NH4)0,4Rb0,6SbF4 FROM NMR AND DSC DATA

V. Ya. Kavun, M. M. Polyantsev, L. A. Zemnukhova, O. V. Brovkina, V. I. Sergienko
Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok, Russia
Keywords: potassium-rubidium (ammonium) tetrafluoroantimonates(III), ion mobility, phase transitions, 19F and 1H NMR spectra

Abstract >>
The NMR and DSC methods are used to study ion mobility and phase transitions in crystalline phases of K0,65Rb0,35SbF4 (I) and (NH4)0,4Rb0,6SbF4 (II). Their 19F and 1H NMR spectra are analyzed to trace the patterns of ion motions in the fluoride and ammonium sublattices at temperatures of 150–500 K and determine the types of motions and the corresponding temperature ranges. The phase transition in compound I is found to lead to a modification in which the dominant type of ion motions is the diffusion of fluoride ions. It is suggested that compounds I and II should demonstrate a conductivity of ≈104102 S/cm at temperatures above 450 K.
																								



18.
CRYSTAL STRUCTURE OF THE IONIC CLUSTER COMPLEX(2,2'-bipyH2)2[Re4Se4(CN)12]·(2,2'-bipy)7H2O

Ya. M. Gaifulin1, A. I. Smolentsev1,2, Yu. V. Mironov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: rhenium, cubane cluster complex, bipyridylium cation, crystal structure

Abstract >>
A rhenium cluster complex (2,2'-bipyH2)2[Re4Se4(CN)12]×(2,2'-bipy)×7H2O (1) is obtained and characterized. The compound crystallizes in a monoclinic space group C2/c with the unit cell parameters: a = 16.9191(6) Å, b = 18.7458(6) Å, c = 19.0139(5) Å, β = 108.568(1)°, V = 5716.6(3) Å3, Z = 4, dx = 2.291 g/cm3. The crystal structure is a packing of bipyridylium cations (2,2'-bipyH2)2+, cluster anions [Re4Se4(CN)12]4–, bipyridyl molecules, and crystal water molecules, which are linked together by a system of hydrogen bonds.
																								



19.
CRYSTAL STRUCTURE OF TETRAMETHYLAMMONIUM FLUORIDOTITANATE(IV) WITH DIMERIC COMPLEX ANIONS OF DIFFERENT COMPOSITIONS

R. L. Davidovich1, V. V. Tkachev2, V. B. Logvinova1, V. I. Kostin1, V. Stavila3
1Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok, Russia
2Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia
3Sandia National Laboratories, Livermore, California, United States
Keywords: thermodynamics crystal structure, fluoridotitanate(IV), tetramethylammonium, dimeric complex anion, octahedron, tetrahedron

Abstract >>
To the best of our knowledge, this is the first report of the synthesis and characterization of tetramethylammonium fluoridotitanate(IV) [N(CH3)4]4[Ti2F11][Ti2F9(H2O)2] with two dimeric complex anions of different compositions. The disordered crystal structure of [N(CH3)4]4[Ti2F11][Ti2F9(H2O)2] is formed by dimeric complex anions [Ti2F11]3– and [Ti2F9(H2O)2] in a 1:1 ratio and tetramethylammonium cations N(CH3)4+, each with an occupancy factor of 0.5. The dimeric complex anions, which structurally alternate with an occupancy factor of 0.5, form a pseudodimeric anion {(Ti2F11)0,5(Ti2F9(H2O)2)0,5}2 whose charge is compensated by the disordered cations N(CH3)4+. The hydrogen bonds OH⋯F link the dimeric complex anions [Ti2F11]3 and [Ti2F9(H2O)2] into polymeric ribbons, with the N(CH3)4+ cations being located between the ribbons.
																								



20.
CRYSTAL STRUCTURAL AND FLUORESCENCE PROPERTIES OF A TWO-DIMENSIONAL COBALTOUS COORDINATION POLYMER CONTAINING BIS(BENZIMIDAZOLE) LIGAND

C. L. Ming, X. Du, L. Qin, G. H. Cui
Hebei United University, Tangshan, Hebei Province, P. R. China
Keywords: 1,4-bis(5,6-dimethyl-benzimidazolyl)-2-butene, Co(II) complex, crystal structure

Abstract >>
A new 2D coordination polymer {[Co(IPA)(L)]×0.25H2O}n (L = 1,4-bis(5,6-dimethyl-benzimidazolyl)-2-butene, H2IPA = 5-hydroxyisophthalic acid) is hydrothermally synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction. The structure analysis indicates that the compound belongs to the orthorhombic system, space group Pnma, a = 17.5256(2) Å, b = 15.2074(2) Å, c = 9.7633(1) Å and Z = 4. The complex possesses a 2D (4, 4) network structure and the adjacent layers are further assembled into a 3D supramolecular framework via intermolecular O—H⋯O hydrogen bond interactions. The luminescent properties of the compound and free ligand L are investigated in the solid state.
																								



21.
RYSTAL STRUCTURE OF A NOVEL CADMIUM SULFATE COORDINATION POLYMER BASED ON THE MULTIDENTATE 2-(3-(4-(PYRIDIN-4-YL)PHENYL)-1H-1,2,4-TRIAZOL-5-YL) PYRIDINE LIGAND

F.-L. Liu, X.-P. Wang, D. Sun
Shandong University, Jinan P. R. China
Keywords: coordination polymer, cadmium complex, sulfate, 2-(3-(4-(pyridin-4-yl)phenyl)-1H-1,2,4-triazol-5-yl)pyridine

Abstract >>
A novel metal-organic coordination polymer, namely [Cd2(Hpptpd)2(SO4)2(H2O)]n (I) (Hpptpd = 2-(3-(4-(pyridin-4-yl)phenyl)-1H-1,2,4-triazol-5-yl)pyridine), is hydrothermally synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction. The X-ray diffraction analysis reveals that I crystallizes in the triclinic system, space group P–1 with a = 8.593(6) Å, b = 9.832(6) Å, c = 11.845(7) Å, α = 68.172(10)°, β = 88.002(12), γ = 84.916(11), V = 925.3(10) Å3, Z = 2. In I, the Cd(II) atom is heptacoordinated and displays a CdN3O4 pentagonal bipyramidal geometry. A pair of head-to-tail arranged Hpptpd ligands with a chelating+bridging mode binds two Cd(II) ions to form a centrosymmetric [Cd2(Hpptpd)2] subunit which is bridged by two centrosymmetric sulfate anions to form a zigzag chain. The interchain Owater—H⋯Osulfate hydrogen bond extend the one-dimensional (1D) chain into a two-dimensional (2D) supramolecular sheet incorporating centrosymmetric twelve-membered R44(12) hydrogen-bonding rings. The adjacent sheets further interdigitate with each other to form the resultant three-dimensional (3D) supramolecular framework by NHpptpdH⋯Osulfate hydrogen bonds and π⋯π stacking interactions.
																								



22.
CRYSTAL STRUCTURE OF NEW (Z)-2-((E)-3-(4-NITROPHENYL)-1-FERROCENYLALLYLIDENE)HYDRAZINE CARBOTHIOAMIDE

N. Wang, Y. Huo
Yancheng, Jiangsu, China
Keywords: X-ray diffraction, monoclinic symmetry, carbothioamide, ferrocenyl

Abstract >>
A new compound of (Z)-2-((E)-3-(4-nitrophenyl)-1-ferrocenylallylidene)hydrazine carbothioamide is synthesized and its crystal structure is determined by single crystal X-ray diffraction. The compound belongs to the monoclinic P21/n space group with the cell parameters: a = 7.6469(6) Å, b = 19.6091(16) Å, c = 12.6534(10) Å, V = 1875.0(3) Å3.
																								



23.
YTTRIUM AND SAMARIUM COMPLEXES WITH A LINKED 1,4,7-TRIAZACYCLONONANE-ARYLOXIDE ANCILLARY LIGAND

J. Cui1,2, I. C. Santos1, J. M. Carretas1
1Universidade de Lisboa, 2696-066, Bobadela LRS, Portugal
2University of Notre Dame, Notre Dame, USA
Keywords: 1,4,7-triazacyclononane (TACN), yttrium, samarium, synthesis, crystal structures

Abstract >>
The reaction of yttrium trichloride with the stoichiometric amount of the potassium salt of the 1-(3,5-di-tert-butyl-2-hydroxybenzyl)-4,7-diisopropyl-1,4,7-triazacyclononane ligand (iPr2-TACN-CH2C6H2t Bu2OH) (TACN = 1,4,7-triazacyclononane) in DME affords in good yield complex [iPr2-TACN-CH2C6H2t Bu2O]YCl2 (1). This complex is characterized by elemental analysis and 1H nuclear magnetic resonance; the solid state structure is determined by the single crystal X-ray diffraction analysis. In complex 1, the metal centre is six-coordinated by the aryloxide oxygen atom, the three nitrogen atoms of the TACN ligand, and two chlorine atoms. The X-ray structure of isomorphic samarium complex [iPr2-TACN-CH2C6H2t Bu2O]SmCl2 (2) is also determined.
																								



24.
CARBONATE HYDROXYLAPATITE SYNTHESIS AND CRYSTALLIZATION ON METALLIC IMPLANTS

R. R. Izmailov, O. A. Golovanova, T. V. Panova
Dostoevsky Omsk State University, Omsk, Russia
Keywords: synthesis, synovial fluid, titanium, carbonate hydroxylapatite, surface treatment, power ion beam, crystallization

Abstract >>
The work deals with the synthesis of carbonate hydroxylapatite from a prototype human synovial fluid. The process of carbonate hydroxylapatite crystallization on the alloys of different composition, roughness, and treatment techniques is studied. The quantitative characteristics measuring the efficiency of coating deposition by biomimetic synthesis from the model solution of human synovial fluid are calculated.
																								



25.
A PHYSICOCHEMICAL STUDY OF THE STRUCTURE, COMPOSITION, AND PROPERTIES OF HYDROXYLAPATITE MODIFIED BY SILICATE IONS

M. V. Berdinskaya1, O. A. Golovanova1, A. V. Zaits1, V. I. Drozdov2, N. N. Leont'eva2, N. V. Anthonicheva3
1Dostoevsky Omsk State University, Omsk, Russia
2Institute of Problems of Hydrocarbon Processing, Siberian Branch, Russian Academy of Sciences, Omsk, Russia
3, Omsk, Russia
Keywords: hydroxylapatite, silicate ions, silicon-containing hydroxylapatite, extracellular fluid, structure, phase composition, bioresorbility

Abstract >>
By deposition from the simulated body fluid solution hydroxylapatite and silicon-substituted hydroxylapatite samples are synthesized. The structure, properties, and phase composition of the obtained compounds are analyzed by a complex of physicochemical methods (powder X-ray diffraction, IR Fourier spectroscopy, TGA, etc.). It is found that during the deposition of the solid phase silicate ions partially substitute for phosphate ions in the structure of hydroxylapatite. The thermal stability and bioresorbility of modified calcium phosphates are studied. The conclusion is drawn that with an increase in the fraction of silicate ions in the structure of silicon-containing apatite an increase in the thermal stability and bioresorbility is observed.
																								



26.
A TEM STUDY OF MoVTe(Nb) OXIDE CATALYSTS FOR THE SELECTIVE CONVERSION OF PROPANE

A. V. Ishchenko1,2, E. V. Ishchenko1,2, T. V. Andrushkevich1
1Boreskov Institute of Catalysis, Siberian Branch, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: transmission electron microscopy, nanosized crystallites, 1 and 2 phases, MoVTe(Nb)O oxide catalysts

Abstract >>
The structure of X-ray amorphous precursors of MoVTeO and MoVTeNbO oxide catalysts and their conversion at high-temperature treatment and under exposition in the reaction medium is studied by analytical transmission electron microscopy (TEM) in combination with the local energy dispersive X-ray (D) microanalysis of the elemental composition. At thermal treatment in the range of 300–450 °C the presence of both true amorphous phases and nanosized crystallites of the orthorhombic 1 and pseudohexagonal 2 phases is detected in the MoVTe(Nb)O catalysts. An increase in the annealing temperature results in the formation of well-crystallized particles of the 1 and 2 phases in the MoVTeNbO catalyst. The four-component 1 phase is stable at 550 C and it is maintained under the reaction conditions. At an increase in the temperature of thermal treatment the successive crystallization of nanosized particles occurs in the three-component MoVTeO system with the formation of mainly the 2 phase. The nanostructured three-component 1 phase formed at low temperatures cannot crystallize into the full 1 phase in the absence of Nb and decomposes with the formation of the 2 phase that is inactive in the conversion of propane. The calculation procedure for D, which was developed specially for these catalysts, enabled the refinement of the chemical composition of separate phases.
																								



27.
DETERMINATION OF ORGANOGENIC ELEMENTS IN THE COMPOSITION OF FUNCTIONAL COMPOUNDS AND MATERIALS

V. P. Fadeeva, V. D. Tikhova, Yu. M. Deryabina, O. N. Nikulicheva
Vorozhtsov Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: elemental analysis, organogenic elements, oxide catalytic compositions, functional compounds and materials

Abstract >>
The presented analysis methods (automatic and gravimetric) are used to determine the main composition of various organic functional materials such as paramagnetic chelating agents for the synthesis of molecular attices, polyfluoroaromatic compounds for the preparation of special attices, new antivirus and analgesic agents, photoinitiator compounds for cationic polymerization, fluorophores for organic light emitting diodes, and so on. Conditions for the quantitative formation of final products of the complete decomposition of the compound (CO2, H2O, N2, SO2) are shown: the application of special oxide catalytic compositions and also the use of selectively adsorbing reagents for the removal of compounds hindering the determination of organogenic elements. Their determination error does not exceed ±0.3 % abs.
																								



28.
A CAPILLARY GAS CHROMATOGRAPHIC ANALYSIS OF THE CHARACTERISTICS OF IONIC LIQUID FILMS

M. V. Shashkov1,2, V. N. Sidelnikov1
1Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: ionic liquids, gas chromatography, stationary phases, diffusion, loading capacity

Abstract >>
Ionic liquid films are a promising material for the preparation of capillary columns in gas chromatography because they provide new opportunities for chromatographic analysis. In this work the properties of ionic liquid films are studied by capillary gas chromatography. Ionic liquids based on 4-methylpyridinium cation and also 1,2-dimethylimidazolium cations are analyzed. For comparison the Carbowax 20M polyethylene glycol film is used. Diffusion properties are studied by determining the dependence of the height equivalent to a theoretical plate on the carrier gas rate. It turns out that the films based on ionic liquids are characterized by shorter diffusion times in comparison with polyethylene glycol. The loading capacity of the films for which ionic liquids proved to be comparable with polyethylene glycol is also determined in the work.
																								



29.
DIAGNOSTICS OF THE STRUCTURE AND COMPOSITION OF ULTRAFINE CARBON OBTAINED BY DETONATION

A. A. Shtertser1, V. Yu. Ulianitsky1, I. S. Batraev1, S. A. Gromilov2,3, A. V. Okotrub2,3, A. I. Saprykin2,3
1Lavrent`ev Institute of Hydrodynamics, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
3Novosibirsk State University, Novosibirsk, Russia
Keywords: acetylene, oxygen, detonation, carbon condensate, ultrafine powders, powder X-ray diffraction analysis, electron microscopy, Raman scattering, electrochemical properties

Abstract >>
A complex of methods is employed to study the properties of carbon condensate obtained by detonation of the enriched acetylene/oxygen mixture. The effect of the gas mixture composition and the methods to initiate detonation, which provide the preparation of ultrafine products, are analyzed. According to the powder X-ray diffraction and electron microscopy data, the detonation products are a carbon condensate consisting of coalescent amorphous particles with a size of ~100 nm.
																								



30.
A STUDY OF PROPERTIES OF THE CHROMATOGRAPHICALLY STRUCTURED SORBENT BASED ON A TRIAZINE POLYMER

Yu. V. Patrushev1,2, V. N. Sidelnikov1
1Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: triazine polymer, ordered micropores, capillary gas chromatography, capillary column

Abstract >>
A new organic sorbent based on a triazine polymer that is a two-dimensional supramolecule with ordered micropores is studied. The possibility to deposit a sorbent layer on the inner surface of a fused silica capillary is shown. The chromatographic properties of columns with the sorbent and the diffusion characteristics of the porous layer are analyzed.
																								



31.
STRUCTURAL EFFECTS IN SECONDARY ION EMISSION OF Fe–30.2%Ni AND Fe36%Ni INVAR ALLOYS

V. P. Ivanov, S. N. Trukhan
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: secondary ion emission, iron-nickel invar alloys, phase magnetic transition

Abstract >>
Experimentally, in the range of 300–700 K, the temperature dependences of secondary ion emission (SIE) for iron-nickel alloys with nickel content of 30.2 % and 36 % are studied by secondary ion mass spectrometry. The observable changes in SIE for iron and nickel ions in the neighborhood of the Curie point are due to magnetic transition, which we hold to be a first-order phase transition. The influence of carbon contained in the alloys manifests itself in the form of SIE peaks at 530630 K.