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Journal of Structural Chemistry

2014 year, number 4

1.
STRUCTURE OF BIAND TRINUCLEAR CLUSTERS OF ALUMINUM IONS AT THE CATIONIC SITES OF MORDENITE

A.V. Larin1,2, G.M. Zhidomirov1,3
1Moscow State University, Russia
2Plasmonika, Ural Building, Skolkovo Center, Moscow oblast, Russia
3Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: aluminum clusters, simulation, mordenite

Abstract >>
The structures and stability of bi- and trinuclear Al clusters at the cationic sites in an 8-membered ring of mordenite are calculated within the cluster approach using the DFT method. Adsorption heats of hydrogen and water, hydrogenation and hydrolysis reactions are compared with similar values for the Ga cluster at the cationic sites of a similar Ga-exchange form of mordenite whose existence is consistent with the experiment. The effect of a different arrangement of lattice aluminum atoms in the 8-membered ring of mordenite is analyzed.



2.
QUANTUM CHEMICAL DFT CALCULATIONS OF THE LOCAL STRUCTURE OF THE HYDRATED ELECTRON AND DIELECTRON

I. I. Zakharov1,2
1Dal' East Ukrainian National University, Lugansk, Ukraine
2Technological Institute, Severodonetsk, Ukraine
Keywords: quantum chemical DFT and РCM calculations, molecular water clusters (H2О)8, (H2О)8 and (H2О)82–, hydrated electron and dielectron models, supermolecule-continuum approximation

Abstract >>
The adiabatic bound state of an excess electron is calculated for a water cluster (H2O)8- in the gas phase using the DFT-B3LYP method with the extended 6-311++G(3df,3pd) basis set. For the liquid phase the calculation is performed in the polarizable continuum model (PCM) with regard to the solvent effect (water, e = 78.38) in the supermolecule-continuum approximation. The value calculated by DFT-B3LYP for the vertical binding energy (VBE) of an excess electron in the anionic cluster (VBE (H2O)8- = 0.59 eV) agrees well with the experimental value of 0.44 eV obtained from photoelectron spectra in the gas phase. The VBE value of the excess electron calculated by РСМ-B3LYP for the (H2O)8- cluster in the liquid phase (VBE = 1.70 eV) corresponds well to the absorption band maximum λmax = 715 nm (VBE = 1.73 eV) in the optical spectrum of the hydrated electron ehydr-. Estimating the adiabatic binding energy (ABE) ehydr- in the (H2O)8- cluster (ABE = 1.63 eV), we obtain good agreement with the experimental free energy of electron hydration ΔG2980 (ehydr-) = 1.61 eV. The local model (H2O)82- of the hydrated dielectron is considered in the supermolecule-continuum approximation. It is shown that the hydrated electron and dielectron have the same characteristic local structure: -O-H{}H-O- and -O-H{↓}H-O- respectively.



3.
STRUCTURAL AND THERMODYNAMIC CONSEQUENCIES OF THE INTERACTION OF CONFORMATIONAL DEGREES OF FREEDOM OF AZOMETHINES IN THE NEMATIC PHASE

E. M. Aver'yanov
Kirenskii Institute of Physics, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russia
Keywords: azomethines, benzylideneaniline, conformation, steric effects of substituents, nematic-isotropic liquid transition, conformational polymorphism

Abstract >>
The interaction of the conformational degrees of freedom of azomethines in the nematic phase, which is induced by electronic donor-acceptor properties of the terminal substituents of the benzylideneaniline core is studied. These degrees of freedom related to the rotation angles φk around the bonds between the substituent and the aniline ring (φ1) and also between the CH=N bridge and the aniline ring (φ2) are characterized by the parameters Qk = cos2φk. It is found that the interaction of these degrees of freedom is manifested in the linear dependence Q2( Q1). Within the phenomenological theory the effect of this interaction on changes δk in the Qk values during the nematic liquid crystal-isotropic liquid phase transition is revealed along with the temperature TNI and character of this transition. The derivation of previously established empirical dependences TNI( Qk ) is presented in the presence of direct and indirect steric effects of side substituents affecting the Qk values. A diverse combination of δk signs in the nematic phase, which is a prerequisite for the conformational polymorphism of the nematic phases of azomethines, is shown.



4.
STRUCTURES, STABILITIES, AND ELECTRONIC PROPERTIES OF AlnAu (n = 1–15) CLUSTERS: A DENSITY FUNCTIONAL STUDY

S.Y. Li, L. Guo, R.J. Zhang, X. Zhang
Shanxi Normal University, Linfen, China
Keywords: AlnAu bimetallic clusters, DFT calculations, relative stability, electronic structure

Abstract >>
We present density functional calculations of AlnAu clusters for n = 1–15. The growth pattern for AlnAu ( n = 1–7, 12, 14, 15) clusters is the Au atom occupying a peripheral position of Aln clusters, and the growth pattern for AlnAu(n = 8, 10 and 13) clusters is Au-substituted Aln+1 clusters. It is found that the Au atom replaces the surface atom of an Aln+1 cluster and occupies a peripheral position. In addition, the ground state structures of AlnAu clusters are more stable than pure Aln clusters. It is found that the Al13Au cluster exhibits high stability.



5.
PROPERTIES OF THE SILVER CYCLIC AMIDE Ag 2(C 4H 4NO 2) 2(H 2O) CRYSTAL FROM THE PERIODIC DFT COMPUTATIONS

A. Stashans, D. Castillo
Universidad Tйcnica Particular de Loja, Apartado 11-01-608, Loja, Ecuador
Keywords: crystal structure, chemical bonding, electronic properties, magnetism, DFT

Abstract >>
A molecular crystal of silver cyclic amide Ag 2(C 4H 4NO 2) 2(H 2O) is studied using first-principles density functional theory calculations within the generalized gradient approximation (GGA). A number of different exchange-correlation functionals are considered for a possible treatment of the system. It is found that the Perdew-Burke-Ernzerhof (PBE) GGA exchange-correlation functionals are adequate for the Ag 2(C 4H 4NO 2) 2(H 2O) crystal. The results obtained show the possibility to reproduce rather well the geometry of at least some molecular crystals by means of the periodic solid-state calculations if the computational parameters are chosen adequately. The present work also reports the analysis of the chemical bonding in the material and gives the total and partial density of states. Our solid-state computations point out the possible magnetic properties of the molecular crystal under study.



6.
DISILINE-DOPED BORON NITRIDE NANOTUBES: A COMPUTATIONAL STUDY

S. Arshadi1, A.R. Bekhradnia2,3, E. Mohammadi1, A. Asghari1
1Payame Noor University, PO Box 19395-3697, Tehran, Iran
2Pharmaceutical Sciences Research Center, Mazandaran University of Medical Sciences, Sari, Iran
3RGothenburg University, Gothenburg, Sweden
Keywords: DFT, Disiline, GIAO, chemical shielding, IGAIM, isotropic, anisotropic

Abstract >>
The properties of the electronic structure of the Disiline-doped boron nitride nanotubes (Disiline-BNNTs) are investigated by a density functional theory (DFT) calculation. The structural forms are firstly optimized and the CS tensors calculated. Subsequently, the chemical-shielding isotropic (CS I) and chemical shielding anisotropic (CS A) parameters are found. The shielding values of boron (B) and nitrogen (N) atoms were calculated by Gauge-Including Atomic Orbital (GIAO), Continuous Set of Gauge Transformations (CSGT) and Individual Gauges for Atoms in Molecules (IGAIM) methods, using B3LYP/6-311+G*. The B3LYP level of theory with IGAIM was the best method to evaluate the theoretical chemical shifts for studied models. The results reveal a significant effect of Disiline doping on the chemical shielding tensors at the sites of those 11B and 15N nuclei located in the nearest neighborhood of the Disiline-doped ring. Furthermore, the values of dipole moments and HOMO-LUMO gaps change in the Disiline-doped models in comparison with the original pristine model.



7.
COMPARATIVE ESTIMATION OF THE ENERGIES OF INTRAMOLECULAR С-H⋯O, N-H⋯O AND О-H⋯O HYDROGEN BONDS ACCORDING TO THE QTAIM ANALYSIS AND NMR SPECTROSCOPY DATA

A.V. Vashchenko, A.V. Afonin
Favorsky Institute of Organic Chemistry, Siberian Branch, Russian academy of Sciences, Irkutsk, Russia
Keywords: внутримолекулярная водородная связь, МР2, QTAIM, RDG, intramolecular hydrogen bond, МР2, QTAIM, RDG

Abstract >>
The energies of intramolecular С-H⋯O, N-H⋯O and О-H⋯O hydrogen bonds in model compounds are empirically estimated based on the values of the hydrogen bond induced weak-field shift of the bridging hydrogen atom signal in the 1Н NMR spectrum. It is supported by a theoretical estimation of these energies based on the electron density value at the hydrogen bond critical point calculated within the QTAIM method. Good agreement between the empirical and theoretical estimates is found, which gives evidence of their reliability. It is shown that from the standpoint of their strength the intramolecular N-H⋯O and О-H⋯O hydrogen bonds can be classified as moderate whereas the intramolecular С-H⋯O hydrogen bonds must be classified as very weak interactions similar in their energy significance to van der Waals interactions.



8.
SPIN RELAXATION AND STRUCTURE OF LIGHT-INDUCED SPIN-CORRELATED PCBM -/P3HT + RADICAL PAIRS

M.N. Uvarov1, A.G. Popov1,2, E.A. Lukina1,2, L.V. Kulik1,2
1Voevodskii Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Russia
Keywords: спин-коррелированная радикальная пара, фуллерены, проводящие полимеры, электронный парамагнитный резонанс, электронное спиновое эхо, spin-correlated radical pair, fullerenes, conducting polymers, electron paramagnetic resonance, electron spin echo

Abstract >>
The electron spin echo (ESE) method is applied to determine the spin relaxation times of long-term light-induced radicals and short-term spin-correlated radical pairs (SCRPs) formed during pulse laser irradiation of a composite consisting of phenyl-С 61-butyric acid methyl ether (PCBM) and poly-(3-hexylthiophene) (P3HT) at 80 K. Dependences of the ESE signal recorded to measure the longitudinal relaxation times of P3HT +/PCBM - SCRPs and the free P3HT + radical are found to be approximated by the dependence of the form exp(-( t/ T 1) 0 . 6) with parameters Т 1 lying in the microsecond range. By means of the instantaneous diffusion model the difference in the transverse spin relaxation times of the P3HT +/PCBM - radical pair at complete and incomplete microwave pulse excitation of the echo-detected EPR spectrum is explained. Based on it, the magnetic interaction energy between the electron spins in P3HT +/PCBM - SCRPs is estimated; E/ ћ ~ 10 6 s -1.



9.
CHLORINE AGGREGATION IN THE SUPRAMOLECULAR STRUCTURE OF CHLOROBENZENE- о-CHLOROTOLUENE SOLUTIONS

A.I. Abramovich, E.S. Alekseev, T.V. Bogdan, L.V. Lanshina
Moscow State University, Moscow, Russia
Keywords: растворы хлорбензол-о-хлортолуол, молекулярное рассеяние света, скорость звука, избыточные функции, молекулярно-динамическое моделирование, хлор-агрегация, контакты Cl…Me, chlorobenzene-о-chlorotoluene, molecular light scattering, speed of sound, excess functions, molecular dynamic simulation, chlorine aggregation, Cl…Me contacts

Abstract >>
An analysis of the concentration dependences of the molecular light scattering parameters in chlorobenzene- о-chlorotoluene solutions shows that the entire concentration range can be split into three intervals with different structural features: 0-0.2 ppm, 0.2-0.9 ppm, and 0.9-1 ppm chlorobenzene. The features are manifest in physicochemical properties such as sound velocity and excess molar volume, adiabatic compressibility, and molar refraction. Experimental data are compared with those obtained by molecular dynamics simulation. It is concluded that the chlorobenzene structure is determined by Cl…Cl interactions while the structuring of liquid o-chlorotoluene and its solutions is largely determined by intermolecular Cl…Me interactions.



10.
H 2O-NH 4Cl SYSTEM: THERMODYNAMICS AND STRUCTURE OF SUPERSATURATED (8ч28 m) SOLUTIONS AT 298.15 K

V. P. Korolev
Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: термодинамика, водный раствор, хлорид аммония, thermodynamics, aqueous solution, ammonium chloride

Abstract >>
Thermodynamic characteristics are determined for supersaturated (8÷28 m ) aqueous ammonium chloride solutions at 298.15 K: activity as well as partial molar enthalpy, volume, and excess entropy of water, osmotic coefficients, density, and salt hydration numbers. The relative humidity above the solution decreases from 75.6% (8 m solution) to 44.7% (28 m solution). A directly proportional dependence is found between the enthalpy and entropy characteristics. The negative values of the nonideal portion of the Gibbs energy are due to structural effects (excess entropy). The excess entropy of water has the same value 1.8 J/(mol×K) in supersaturated 12 m NaCl and 28 m NH 4Cl. The ratio 12/28 = 3/7 is also valid for other "isoentropic" molalities of the said salts.



11.
BEHAVIOR OF MICROPOROUS ZIRCONOSILICATE HILAIRITE UNDER HIGH PRESSURE

Yu. V. Seryotkin1,2, V. V. Bakakin3, I. V. Pekov4
1Sobolev Institute of Geology and Mineralogy, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Russia
3Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
4Moscow State University, Russia
Keywords: к цирконосиликат, илерит, кристаллическая структура, высокое давление, zirconosilicate, hilairite, crystal structure, high pressure

Abstract >>
The behavior of natural zeolite-like hetero-framework zirconosilicate hilairite |Na 1.47H 0.53(H 2O) 2.7| [ZrSi 3O 9] is studied by single crystal X-ray diffraction at a high pressure (up to 4.73 GPa): space group R3, a = 10.5667(2) Å, c = 15.9109(4) Å, V = 1538.54(6) Å 3, Z = 6. The compression of hilairite is practically isometric in the whole pressure range studied and is close to linear. Above 3.5 GPa an increasing deterioration of the single crystal is observed, which is interpreted as the started first order phase transition accompanied by significant volumetric changes.



12.
STUDY OF ACID PYRIDINE-3-CARBOXYLIC ACID DODECATUNGSTENPHOSPHATE OF THE COMPOSITION (C 6NO 2H 5) 2Н[PW 12O 40]Ч2Н 2О

G.Z. Kaziev1, O.A. Kirichenko1, A.I. Stash2, H. Quinones Saul3, E.A. Solov’eva1, Y.S. Chen4
1Moscow State Pedagogical University, Moscow, Russia
2L.Ya. Karpov Institute of Physical Chemistry, Moscow, Russia
3UAM, Ascapotzalco, Mexico
4The University of Chicago, Chicago, Illinois, United States
Keywords: гетерополисоединения, рентгеноструктурный анализ, физико-химические свойства, heteropolycompounds, X-ray crystallography, physicochemical properties

Abstract >>
Acid pyridine-3-carboxylic acid dodecatungstenphosphate (С 6NO 2H 5) 2H[PW 12O 40]×2Н 2О is synthesized. The compound is studied by chemical analysis, IR spectroscopy, X-ray crystallography, and thermogravimetry. The compound is found to crystallize at 290 K in a hexagonal crystal system (sp. gr. R -3) (I) with the unit cell parameters: а = 33.015(6) Å, с = 12.010(2) Å, g = 120°, V = 11337(4) Å 3, Z = 9. When the temperature decreases to 100 K, a phase transition is observed leading to an increase in symmetry to R -3 m (II), with the unit cell parameters: а = 33.072(1) Å, с = 24.234(1) Å, g = 120°, V = 22955(2) Å 3, Z = 18.



13.
STRUCTURE AND PROPERTIES OF TRIPYRIDINE NITROSOCOMPLEXES OF RUTHENIUM: mer-[Ru(NO)Py 3Cl(OH)]ClЧ1.5H 2O AND mer-[Ru(NO)Py 3Cl(H 2O)]Cl 2Ч2H 2OЧ0.5HCl

A.N. Makhinya1,2, M.A. Il’in1,2, I.A. Baidina1, P.E. Plyusnin1,2, M.R. Gallyamov1
1Nikolaev Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberian Branch, Novosibirsk, Russia
2Novosibirsk state university, Russia
Keywords: нитрозокомплексы, рутений, аминокомплексы, пиридин, рентгеноструктурный анализ, ИК спектроскопия, ЯМР, термогравиметрия, nitrosocomplexes, ruthenium, amine complexes, pyridine, X-ray crystallography, IR spectroscopy, NMR, thermal analysis

Abstract >>
Reaction of K 2[Ru(NO)Cl 5] with pyridine in aqueous ethanol at pH ~ 7-8 affords a nitrosoruthenium hydroxocomplex mer -[Ru(NO)Py 3Cl(OH)]Cl×1.5H 2O (I), yield ~55 %. The treatment of the hydroxocomplex I with hydrochloric acid at room temperature gives the aqua complex mer -[Ru(NO)Py 3Cl(H 2O)]Cl 2×2H 2O×0.5HCl (II). The structures of the compounds have been determined by X-ray crystallography: I - sp. gr. P 2 1/ n , a = 9.2292(4), b = 11.7781(4), c = 17.4915(7) Å, β = 90.9560(10)°, R = 4.84%; II - sp. gr. P -1, a = 7.3528(9), b = 11.5793(11), c = 13.6961(16) Å, α = 84.558(3), β = 87.668(4), γ = 74.146(4)°, R = 6.22%. Compounds I and II have been characterized by powder XRD, 1Н and 13С NMR, as well as IR spectroscopy. Thermal decomposition of compound II in inert atmosphere has been examined with thermal analysis.



14.
Unusual layer structure in an ion-paired compound containing tetra(isothiocyanate)cobalt(II) dianion and 4-nitrobenzylpyridinium: crystal structure and magnetic properties

H.-Q. Ye, Y.-Y. Li, R.-K. Huang, X.-P. Liu, W.-Q. Chen, J.-R. Zhou, L.-M. Yang, C.-L. Ni
Institute of Biomaterial, South China Agricultural University, Guangzhou, P. R. China
Keywords: 1-(4ў-nitrobenzyl)pyridinium, tetra(isothiocyanate)cobalt(II) anion, layer structure, magnetic properties

Abstract >>
A new ion-paired compound [4NO 2BzPy] 2[Co(NCS) 4] (1) ([4NO 2BzPy] + = 1-(4'-nitrobenzyl)pyridinium, NCS - = isothiocyanate) is synthesized and characterized by elemental analysis, IR and UV-Vis spectra, ESI-MS and single crystal X-ray diffraction. Compound 1 is orthorhombic, space group Pbcn, with a = 13.188(2) Å, b = 8.458(1) Å, c = 29.281(4) Å, V = 3266.2(7) Å 3, D calcd = 1.468 g/cm 3, Z = 4, F(000) = 1476, R 1 = 0.0332. The [Co(NCS) 4] 2- anions form an unusual layer structure by S⋯N and S⋯Co interactions, while the [4NO 2BzPy] + cations stack into a 1D column by the p⋯π stacking interaction in the solid state of 1. A magnetic measurement in the range 2-300 K shows a weak antiferromagnetic exchange with θ = -2.42 K in 1.



15.
DICHLOROTRIETHYLPHOSPHINE-[ N-FORMYL- N, Nў-bis(3,4-DIMETHOXY)BENZYL-TRIMETHYLENEDIAMINE]PLATINUM(II)

O. Şahin1, E.O. Ozcan2, N. Gurbuz2, I. Ozdemir2, O. Buyukgungor3
1Scientific and Technological Research Application and Research Center, Sinop University, Sinop, Turkey
2İnцnь University, Malatya, Turkey
3Ondokuz Mayıs University, Samsun, Turkey
Keywords: tetrahydropyrimidine, N-formyl-N,N'-bisaryltrimethylenediamine, Pt(II) complex, X-ray diffraction analysis

Abstract >>
By treatment of 1,3-bis(3,4-dimethoxybenzyl)-3,4,5,6-tetrahydropyrimidinium chloride (1) with KOBu t and [PtCl 2(PEt 3) 2] 2 N -coordinated platinum complex (2) is obtained. The Pt atom is coordinated in square planar arrangements by two chloride ions in a trans-configuration, the N-formyl- N, N'-bisaryltrimethylenediamine nitrogen atom, and the phosphine P atom. An extensive three-dimensional network of three C-H⋯O hydrogen bonds, two C-H⋯π and one π⋯π interactions are responsible for the crystal stabilization. Intermolecular hydrogen bonds and C-H⋯π interactions produce R 2 2(6), R 2 2(22), R 2 2(24), R 3 3(23), R 4 4(26), and R 4 4(32) rings.



16.
FLUORESCENCE AND CRYSTAL STRUCTURES OF NEW MERCURY(II) MACROCYCLIC N-HETEROCYCLIC CARBENE COMPLEXES WITH ETHER CHAINS

J.-W. Wang, M.-C. Zhang
Shanxi Normal University, Linfen, P. R. China
Keywords: mercury, N-heterocyclic carbene, fluorescence, X-ray structure

Abstract >>
Polyerther-linked mercury(II) carbene complexes are synthesized by the reaction of carbene precursores with mercury(II) acetate. The binuclear carbene complexes with the chloride ion linkage are easily prepared by the reaction of mononuclear mercury carbene complexes with tetrabutylammoium chloride. The crystal structures reveal that the fluorescence of mercury complexes are related to the coordination mode of the ligands.



17.
CRYSTAL STRUCTURE OF 2,4,6,8,10,12-HEXANITRO-2,4,6,8,10,12-HEXAAZAISOWURTZITANE SOLVATE WITH ε-CAPROLACTAM

S.M. Aldoshin, Z.G. Aliev, T.K. Goncharov
Institute of Chemical Physics Problems, Russian Academy of Sciences, Chernogolovka, Russia
Keywords: 2,4,6,8,10,12-гексанитро-2,4,6,8,10,12-гексаазаизовюрцитан, полициклический нитроамин, ε-капролактам, рентгеноструктурный анализ, кристаллическая и молекулярная структура, 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, polycyclic nitroamine, ε-caprolactam, X-ray crystallography analysis, crystal and molecular structure

Abstract >>
The crystal structure of the CL-20 solvate with e-caprolactam in the 1:6 ratio is obtained and studied.



18.
1-METHYL-2-((1 E,3 E)-4-PHENYLBUTA-1,3-DIENYL)PYRIDINIUM IODIDE: SYNTHESIS, CHARACTERIZATION, AND X-RAY ANALYSIS

S. Chantrapromma1, N. Boonnak1, N. Kaewmanee1, P. Ruanwas1, H.-K. Fun2,3
1Prince of Songkla University, Hat-Yai, Songkhla, Thailand
2King Saud University, Riyadh, Saudi Arabia
3Universiti Sains Malaysia, Penang, Malaysia
Keywords: crystal structure, pyridinium, quaternary ammonium compound (QAC), π stacking, π-π interaction

Abstract >>
1-Methyl-2-((1 E ,3 E )-4-phenylbuta-1,3-dienyl)pyridinium iodide ( 1) is synthesized and characterized by UV-Vis, FT-IR, 1H and 13C NMR, and single crystal X-ray diffraction. Compound 1 crystallizes in an orthorhombic Iba2 space group with the unit cell parameters a = 12.8236(11) Å, b = 20.1216(17) Å, c = 11.2071(10) Å, V = 2891.8(4) Å 3 and Z = 8. X-ray diffraction indicates that the molecule of 1 displays E , E configurations with respect to the two middle C=C double bonds. The molecular structure of 1 is twisted and the dihedral angle between the pyridinium and phenyl rings is 15.0(2)°. In the crystal packing, cations form stacks in an anti-parallel V-shaped manner along the a axis through π-π interactions between pyridinium and phenyl rings.



19.
STRUCTURE AND CHARACTERIZATION OF A 2D COBALT(II) COMPLEX [Co(L) 2] n (L = 3-NITRO-5-(pyridine-4-YL)BENZOATE)

D.-Y. Ma, H.-F. Guo, L. Qin
Zhaoqing University, Zhaoqing, P. R. China
Keywords: cobalt(II) coordination polymer, hydrothermal synthesis, crystal structure, thermal behavior

Abstract >>
The self-assembly of unsymmetrical tecton 3-nitro-5-(pyridin-4-yl)benzoic acid (HL)with cobalt chloride under hydrothermal conditions affords a new 2D coordination polymer [Co(L) 2] n ( 1, L = 3-nitro-5-(pyridin-4-yl)benzoate), which is characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction analysis, and single crystal X-ray diffraction. Compound 1 is of the triclinic system, space group P-1 with a = 9.7857(12) Å, b = 10.3417(13) Å, c = 10.8463(13) Å, α = 85.155(2)°, β = 74.785(2)°, γ = 88.962(2)°, V = 1055.4(2) Å 3. The crystal structural analysis of complex 1 shows that the cobalt center is six-coordinated in an octahedral geometry by four O atoms from four different L ligands and two N atoms from two different L ligands; the Co(II) cations are bridged by μ 3- L into an interesting two-dimensional network structure. It should be pointed out that the thermal analysis results indicate that complex 1 is quite stable up to 420 °C.



20.
STUDY OF NEW MOLECULAR AND CRYSTAL STRUCTURES OF 4,4,10,10-TETRAMETHYL-1,3,7,9-TETRAAZOSPIRO[5.5]UNDECANE-2,8-DIONE AND ITS SALTS: MONOCHLORIDE, MONONITRATE, AND TETRAIODOTELLURATE

E.E. Netreba1, E.S. Papayanina2
1V.I. Vernadsky Taurida National University, Simferopol, Russia
2L.M. Litvinenko Institute of Physical Organic Chemistry and Coal Chemistry, National Academy of Sciences of Ukraine, Donetsk, Ukraine
Keywords: спиробисмочевина, спирокарбон, моногидрат, монохлорид, мононитрат, тетраиодотеллурат, ЯМР Н, ИК, структура, РСА, РФА, spirobisurea, spirocarbone, monohydrate, monochloride, mononitrate, tetraiodotellurate, Н NMR , IR, structure, single-crystal XRD, powder XRD

Abstract >>
This is the first work to synthesize 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione monohydrate, monochloride, mononitrate, and teteraiodotellurate: C 11H 20N 4O 2×H 2O ( I), C 11H 21N 4O 2 +×Cl - ( II), C 11H 21N 4O 2 +×NO 3 - ( III), and 2(C 11H 21N 4O 2 +)×TeI 4 2-×C 3H 6O ( IV) and determine their structures. Crystals of I are monoclinic: sp. gr. P 2 1/ c , at 298 K a = 5.7118(7), b = 17.842(2), and c = 13.5905(16) Å; β = 91.621(11)°; V = 1384.5(3) Å 3; d x = 1.239 g/cm 3, Z = 4. Crystals of II are tetragonal: sp. gr. P4 3, at 298 K a = 6.4134(3) and c = 34.292(2) Å; V = 1410.47(14) Å 3; d x = 1.303 g/cm 3; Z = 4. Crystals of III are triclinic: sp. gr. P-1, at 298 K a = 8.7614(14), b = 9.3904(18), and c = 10.028(2) Å; α = 63.27(2), β = 78.591(16), and γ = 84.308(15)°; V = 722.3(2) Å 3; d x = 1.40 g/cm 3; Z = 2. Crystals of IV are triclinic: sp. gr. P -1, at 100 K a = 10.4630(4), b = 11.9372(6), and c = 16.4118(5) Å; α = 72.058(3), β = 76.406(3), and γ = 87.029(3)°; V = 1895.04(12) Å 3; d x = 2.06 g/cm 3; Z = 2. The synthesis of s- and p-metals with spirocarbone in acetone medium is found to be impossible due to the protonation by the oxygen atom of the carbonyl group. The main crystalline product of the complexation reaction is a monosalt. Evidence is provided that the recrystallization and drying of the synthesized spirocarbone preparation yields monohydrate ( I); its purity and monophasity is confirmed by a Rietveld refinement of the powder X-ray pattern. The lattice parameters at room temperature are: a = 5.6885(12), b = 17.8496(12), and c = 13.518(3) Å; β = 91.449(15)°; V = 1372.1(4) Å 3. The sample is monophasic.



21.
CRYSTAL STRUCTURE OF A NEW MODIFICATION OF CYANIDE-BRIDGED COPPER(I) COORDINATION COMPOUND CuCN(bpy)] n

A.V. Ermolaev1, A.I. Smolentsev1,2, Yu.V. Mironov1,2
1Nikolaev Institute of Inorganic Chemistry, Russian Academy of Sciences, Siberian Branch, Novosibirsk, Russia
2Novosibirsk State University, Russia
Keywords: цианидный комплекс, медь(I), гидротермальный синтез, кристаллическая структура, cyanide complex, copper (I), hydrothermal synthesis, crystal structure

Abstract >>
The hydrothermal reaction of CuCN and bpy in the presence of an octahedral cluster complex K 2.75Cs 1.25[Re 6Se 8(CN) 4(OH) 2]×H 2O affords a cyanide-bridged chain coordination polymer [CuCN(bpy)] n (bpy - 2,2’-bipyridyl) ( 1). The structure is monoclinic, space group C 2/ c , a = 22.848(2) Å, b = 7.7182(8) Å, c = 14.4331(13) Å, β = 127.805(2)°, V = 2010.9(3) Å 3, Z = 8, d x = 1.623 g/cm 3. Copper atoms have a tetrahedral coordination environment formed by N atoms of the bpy molecule as well as N and C atoms of ambidentate bridging CN ligands.



22.
CRYSTAL STRUCTURE, THERMAL AND FLUORESCENT PROPERTIES OF A 1D Cd(II) COORDINATION POLYMER BASED ON THE BIS(BENZIMIDAZOLE) LIGAND

X. Du, Y.Y. Wang, Y.Q. Zhao, G.H. Cui
Hebei United University, Tangshan, Hebei Province, P. R. China
Keywords: cadmium(II), bis(benzimidazole), hydrogen bond, fluorescent property

Abstract >>
A 1D cadmium (II) coordination polymer {[Cd 2(L) 3Cl 3]×Cl} n (1) (L = 1,3-bis(benzimidazol-l-yl)-2-propanol) is synthesized by the hydrothermal reaction and characterized by elemental analysis, IR, TG, and X-ray single crystal diffraction. Compound 1 crystallizes in the hexagonal system, space group P 63/ m with a = 15.4857(11) Å, b = 15.4857(11) Å, c = 14.478(2) Å, γ = 120°, V = 3006.8(5) Å 3, Z = 2. In the structure of complex 1, each cadmium center is hexahedrally coordinated by three chlorine atoms and three nitrogen atoms of three distinct L ligands. A detailed analysis reveals that compound 1 exhibits a 1D chain of beads and the adjacent chains are further linked by C-H⋯Cl hydrogen bonding to form a 2D supramolecular framework. Furthermore, the solid-state fluorescent property of 1 is investigated at room temperature.



23.
CRYSTAL STRUCTURE AND FLUORESCENT PROPERTIES OF A 2D CADMIUM COORDINATION POLYMER

X. Du, Y.Y. Wang, Y.Q. Zhao, G.H. Cui
Hebei United University, Tangshan, Hebei Province, P. R. China
Keywords: Cd(II), 1,3,5-benzenetricarboxylic acid, binodal(3,5)-connected, π-π stacking interactions

Abstract >>
A new 2D cadmium(II) coordination polymer {[Cd(MBD)(L)]×(H 2O) 2} n ( 1) (H 2MBD = 5-methoxycarbonyl-benzene-1,3-dicarboxylic acid, L = 1,3-bis(benzimidazol-l-yl)-2-propanol) is synthesized, in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during the synthesis. In the structure of complex 1, each cadmium center is octahedrally coordinated by four O atoms from three carboxylate groups and two N of distinct L ligands. A detailed structural analysis reveales that compound 1 exhibits a unique 2D binodal (3,5)-connected (4 2.6 7.8)(4 2.6) topology structure. Furthermore, the 2D layer is extended into a 3D network through π-π stacking interactions. The solid-state fluorescence properties of 1 are investigated at room temperature.



24.
AN ALGORITHM TO IDENTIFY THE EXISTENCE AND REPRODUCIBLY OBTAIN SINGLE CRYSTALS OF SALTS AND MIXED CRYSTALS OF AMINO ACIDS SUITABLE FOR SINGLE-CRYSTAL XRD AND RAMAN SPECTROSCOPY EXPERIMENTS

S.G. Arkhipov1,2, E.V. Boldyreva1,2
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: аминокислоты, смешанные кристаллы, получение монокристаллов, "streak seeding", рентгеноструктурный анализ, КР спектроскопия, amino acids, mixed crystals, single crystal growing, "streak seeding", X-ray crystallography, Raman spectroscopy

Abstract >>
An algorithm is proposed to reproducibly obtain single crystals of salts and mixed crystals of amino acids with dicarboxylic acids and other small organic molecules. The resulting crystals are of high quality and have good faceting, which makes them suitable for single-crystal XRD and Raman spectroscopic (including polarized radiation) experiments. The ease of the implementation and the possibility to reproduce the crystallization using equipment and materials that are available at virtually every laboratory are the hallmarks of the proposed algorithm, which involves two stages of work. During the first stage, the original components are screened, quickly and easily, to find new phases. The aim of the second stage is to obtain single crystals that meet the requirements of different research methods. An ideal case is the one whereby it is possible to control the size of well-faceted spaced apart crystals that grow within a few hours and are easy to separate from the surface.



25.
A SMALL-ANGLE X-RAY SCATTERING STUDY OF THE NANOSTRUCTURAL FEATURES OF HIGH-ASH CARBON MATERIALS

Yu. V. Larichev1,2, A. P. Koskin1, P. M. Eletskii1, S. A. Poluyanov1, F. V. Tuzikov1,2, A. V. Ishchenko1, D. A. Zyuzin1
1Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Russia
Keywords: углерод-кремнеземные композиты, просвечивающая электронная микроскопия, рентгеновская дифрактометрия, малоугловое рентгеновское рассеяние, контрастирование, carbon-silica composites, transmission electron microscopy, X-ray diffraction, small-angle X-ray scattering, masking liquid

Abstract >>
Nanostructured carbon-silica composite materials are prepared from different compounds in one-pot. They are characterized by BET, transmission electron microscopy, X-ray diffraction, and small-angle X-ray scattering. An effective method of the quantitative analysis of the structural dispersed characteristics of the template phase of silica in these composites is proposed.



26.
AN XPS STUDY OF THE INTERACTION OF MODEL Ba/TiO 2 AND Ba/ZrO 2 NSR CATALYSTS WITH NO 2

M.Yu. Smirnov1, A.V. Kalinkin1, D.A. Nazimov1,2, V.I. Bukhtiyarov1,2, E.I. Vovk1,3, E. Ozensoy3
1Boreskov Institute of Catalysis, Siberian Branch, Novosibirsk, Russia
2Novosibirsk State University, Russia
3Bilkent University, Bilkent, Ankara, Turkey
Keywords: модельные NSR катализаторы, реакция с NO , нитрит бария, нитрат бария, рентгеновская фотоэлектронная спектроскопия, model NSR catalysts, reaction with NO , barium nitrite, barium nitrate, X-ray photoelectron spectroscopy

Abstract >>
X-ray photoelectron spectroscopy is used to study the interaction of model NO 2 storage-reduction catalysts (NSR catalysts) Ba/TiO 2 and Ba/ZrO 2 with NO 2. The catalysts are prepared on the surface of ultrathin Al 2O 3 film substrates obtained by the FeCrAl alloy oxidation. It is shown that at room temperature the model catalysts react with NO 2 with the successive formation of surface barium nitrite and nitrate. The NO 2 reduction with the formation of barium nitrite at the initial step of the interaction is assumed to be accompanied by the oxidation of residual metallic barium and amorphous carbon impurity. It is found that the formation of barium nitrate proceeds more efficiently on Ba/ZrO 2 rather than on Ba/TiO 2.



27.
FEATURES OF THE COMPOSITION AND STRUCTURAL TRANSFORMATIONS OF MANGANESE MINERALS OF THE BOL’SHOE MIASSOVO LAKE (SOUTH URAL)

N.A. Palchik, T.N. Moroz, T.N. Grigorieva
Sobolev Institute of Geology and Mineralogy, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: структура, химический состав, свойства, марганцевые минералы, воздействие температур, рентгенография, ИК спектроскопия, structure, chemical composition, properties, manganese minerals, temperature effect, X-ray diffraction, IR spectroscopy

Abstract >>
The mineral and microelement composition of natural manganese minerals from iron-manganese concretions of the Bol’shoe Miassovo lake (South Ural) is investigated. The structural transformations of the samples under the effect of different temperatures are studied. Apart from layered 9.6 Å and 7.2 Å structures of manganese minerals the lake samples often contain various manganese-containing carbonates. For carbonate minerals by IR spectroscopy the dependence of the wavenumbers of n 2 and n 4 vibrations of the СО 3 group on the mineral composition is analyzed. The composition of macro- and microelements of iron-manganese concretions of Bol’shoe Miassovo lake varies in wide ranges not only in different samples, but also in different parts of the same sample. An analysis of the microstructure of lake manganese concretions revealed their biomorphic nature that is exhibited in globe-shaped to filament organic bacterial forms.



28.
A STUDY OF THE THERMAL DECOMPOSITION OF LAYERED PEROVSKITE-LIKE OXIDES ANdTiO 4 AND A 2Nd 2Ti 3O 10 (A = Na, K)

A.M. Sankovich, I.A. Zvereva
St.Peterburg State University, Russia
Keywords: перовскитоподобные слоистые титанаты, термическая стабильность, порошковая рентгеновская дифракция, perovskite-like layered titanates, thermal stability, powder X-ray diffraction

Abstract >>
The thermal stability of cation-ordered perovskite-like layered titanates ANdTiO 4 and A 2Nd 2Ti 3O 10 (A = Na, K) is studied in the temperature range of 900-1400°C. The structural chemical mechanism of their thermal decomposition is established. A comparative analysis of the thermal stability of compounds with different thicknesses of the perovskite layer and different nature of the alkali cation is performed. The observed thermal behavior is explained from crystal chemical standpoints.



29.
COMPOSITION AND STRUCTURE OF LOW-TEMPERATURE NATURAL CARBONATES OF THE CALCITE-DOLOMITE SERIES

И.P. Solotchina, P.A. Solotchin
Sobolev Institute of Geology and Mineralogy, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: кристаллохимия, карбонаты, ряд кальцит-доломит, рентгенография, ИК спектроскопия, озерные осадки, палеоклимат, crystal chemistry, carbonates, calcite-dolomite series, X-ray diffraction, IR spectroscopy, laсustrine sediments, paleoclimate

Abstract >>
Mineralogical and crystallochemical studies of endogenic carbonates from bottom sediments of some shalllow saline lakes of Western Transbaikalia are performed. X-ray diffraction (XRD), IR spectroscopy, electron microscopy, elemental analysis (SR XFA), analysis of stable δ 18O and δ 13С isotopes, and other methods are applied. By modeling the complex XRD profiles by means of the Pearson VII function Mg-calcites with different Mg concentrations and Сa-excess dolomites are found in the assemblage of carbonate minerals. It is shown that in a series of Mg-calcites there is a gap in the region 2θ Cu K a = 30°, which is caused by a transition from the structures representing true solid solutions to the structures of layered “domain” nanosized crystals. The idea of excess-Са dolomite as the extreme member of the Mg-calcite series is substantiated. The carbonate record containing data on the stratigraphical distribution of endogenic carbonates of the calcite-dolomite series is obtained. The amount and ratio of phases with different Mg concentrations in this series are determined by the value of the Mg/Ca ratio, the total salinity and alkalinity of lake waters in the past, changing in accordance with climate cycles and fluctuations of the lake level.



30.
SMALL-ANGLE X-RAY STUDIES OF THE GaAs 0.7Se 0.3 SOLID SOLUTION AT ENERGIES CLOSE TO As AND Se ABSORPTION EDGES

M.D. Sharkov, M.E. Boiko, A.M. Boiko, A.V. Bobyl, S.G. Konnikov
Ioffe Physical Technical Institute, St. Petersburg, Russia
Keywords: малоугловое рассеяние рентгеновских лучей (МУРР), край поглощения, арсенид галлия, селенид галлия, мозаичная структура, small-angle X-ray scattering (SAXS), absorption edge, gallium arsenide, gallium selenide, mosaic structure

Abstract >>
The possibility of a simultaneous use of X-ray diffraction and X-ray absorption techniques in order to characterize the sizes, shapes, and chemical composition of grains in a sample (the solution of the extended uncertainty problem due to the Babinet principle) is shown. A sample of the GaAs 0.7Se 0.3/GaAs solid solution is investigated on the developed laboratory device for a simultaneous performance of X-ray diffraction and X-ray absorption experiments. It is shown that the GaAs 0.7Se 0.3 sample decomposes into separate GaAs and GaSe domains forming a mosaic structure. The sizes of GaAs and GaSe domains are estimated. Components with a linear geometry are sometimes revealed in the composition of GaSe grains.



31.
COMBINED DIAGNOSTICS OF THE STRUCTURE OF COMPLEX OXIDE MATERIALS AND METAL CATALYSTS BY SYNCHROTRON X-RAY DIFFRACTION

A. N. Shmakov1,2, O. Yu. Pod’yacheva1
1Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: синхротронное излучение, дифракция, кислородная проводимость, углеродные нановолокна, synchrotron radiation, diffraction, oxygen conductivity, carbon nanofibers

Abstract >>
The combined use of different synchrotron radiation (SR) X-ray diffraction techniques is shown to be effective in collecting the most complete structural information about an object being studied. The high intensity of SR and its spectral-angular distribution enable researchers to conduct experiments with high angular resolution, experiments using resonance effects, time-resolved experiments, and experiments where the sample is exposed to the effects of temperature and reaction medium. Results are presented of two studies where the distinctive features of SR play the key role.