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Journal of Structural Chemistry

2014 year, number 2

1.
AB INITIO STUDY OF STRUCTURAL AND ELECTRONIC PROPERTIES OF ZIGZAG GRAPHENE NANORIBBONSON HEXAGONAL BORON NITRIDE

V. V. Ilyasov1, V. Ch. Nguyen1, I. V. Ershov1, D. Ch. Nguyen2
1Don State Technical University, Rostov-on-Don, Russia
2Hanoi University of Science and Technology, Hanoi, Vietnam
Keywords: band structure, heterostructure, hexagonal boron nitride, graphene nanoribbons, electronic properties, magnetic moments

Abstract >>
Results of the study of structural and electronic properties of the 8-ZGNR/h-BN(001) heterostructure by the pseudopotential method using plane waves within density functional theory are presented. Within one approximation the features of the spin state at the Fermi level are studied along with the role of the edge and substrate effects in the opening of the energy gap in the 8-ZGNR/h-BN(001) heterostructure in both ferromagnetic and antiferromagnetic orderings. The effect of a substrate made of hexagonal boron nitride was found for the first time. It consists in the opening of the energy gap in the p electron spectrum of the 8-ZGNR/h-BN(001) heterostructure for the ferromagnetic spin ordering. It is shown that the gap was 30 meV. Contributions of the edge effects of the graphene nanoribbon and the substrate to the energy gap formation are differentiated for the first time. It is found that in the 8-ZGNR/h-BN(001) heterostructure the dominant role in the opening of the energy gap at the Fermi level is played by the edge effects. However, when the nanoribbon width decreases, e.g., to six dimmers the substrate role in the gap opening increases and amounts to 45%. Local magnetic moments of carbon atoms are estimated. It is shown that small magnetic moments are induced on boron and nitrogen atoms at the interface.



2.
A QUANTUM CHEMICAL STUDY OF TRIMETHOXYALUMINUM COMPLEXES WITH NEUTRAL MOLECULES

N. V. Alekseev
State Research Institute of Chemistry and Technology of Organoelement Compounds, Moscow, Russia
Keywords: alumoxanes, complexes, quantum chemistry, AIM method, NBO method

Abstract >>
The spatial and electronic structures of trimethoxyaluminum complexes with neutral molecules are calculated by the MP2/6-31(2d,p) method using the PC GAMESS-Firefly program package. The main characteristics of aluminum bonds in these molecules are determined by AIM and NBO methods. It is shown that these bonds can be characterized as the bonds between the atoms with closed shells.



3.
NON–EMPIRICAL QUANTUM CHEMICAL CALCULATIONS OF THE STRUCTURE OF A HOMOLOGOUS SERIES OF NALKYLPYRIDINIUM CATIONS

N. I. Belotserkovets, V. M. Nikolskii
Tver State University, Tver, Russia
Keywords: non-empirical calculation methods, N-alkyl pyridinium, geometry optimization, conformation, total energy, partial atomic charges, dipole moments, frontier orbitals

Abstract >>
The results of non-empirical quantum chemical calculations of geometric parameters, total energies, partial atomic charges, dipole moments, energies of frontier molecular orbitals obtained within second order Möller-Plesset perturbation theory in the MP2/6-31G(d,p) approximation are presented for a homologous series of N-alkyl pyridinium cations containing from 1 to 16 carbon atoms in the hydrocarbon radical. Differences are found in the electronic structure of lower and higher homologues.



4.
AB INITIO STUDY OF DEHALOHYDROGENATION REACTION OF 2–HALO2,3DIHYDROPHOSPHININE

H. Shirani Il Beigi1, M. Nikbakht2, P. Ghanbar pour2
1Islamic Azad University, Najaf Abad, Isfahan, Iran
2Novel Drug Delivery Research Center, Kermanshah University of Medical Sciences, Kermanshah, Iran
Keywords: ab initio, NBO, NICS, 2-halo-2, 3-dihydrophosphinines

Abstract >>
Decomposition of 2-fluoro-2,3-dihydrophosphinine (1), 2-chloro-2,3-dihydrophosphinine (3), 2-bromo-2,3-dihydrophosphinine (5) to phosphinine was investigated using Molecular orbital and density functional theory. Study on the B3LYP/6-311+G** level of theory revealed that the required energy for the decomposition of compounds 1, 3 and 5 to phosphinine is 30.56, 28.23 and 24.03 kcal×mol–1, respectively. HF/6-311+G**//B3LYP/6-311+G** calculated barrier height for the decomposition of compound 1, 3 and 5 to phosphinine is 57.56, 37.26 and 30.77 kcal×mol–1, respectively. Also, MP2/6-311+G**//B3LYP/6-311+G** results indicated that the barrier height for the decomposition of compound 1, 3 and 5 to phosphinine is 46.59, 47.28 and 42.57 kcal×mol–1, respectively. Natural bond orbital (NBO) population analysis and nuclear independent chemical shift (NICS) results showed that, reactants are non-aromatic but products of elimination reaction are aromatic, C-H and C-X bonds are broken and H-X bond is appear.



5.
MOLECULAR PARAMETERS FOR GAS CHROMATOGRAPHICIDENTIFICATION OF E AND Z–ISOMERS OF UNSATURATED COMPOUNDS

I. G. Zenkevich
St. Petersburg State University, St. Petersburg, Russia
Keywords: unsaturated compounds, E- and Z-isomers, gas chromatographic retention indices, molecular topological parameters, pentadecenes, octadienes, methyl octadecenoates, identification

Abstract >>
The use of the previously proposed parameter U proportional to the vibrational component of intramolecular energies, which can be considered as a kind of molecular topological characteristics, enables the estimation of gas chromatographic retention indices of isomeric unsaturated compounds. The latter include both isomers differing in the position of = double bonds in the carbon skeleton of the molecules and isomers with different configurations of these bonds (E and Z).



6.
AN X-RAY ABSORPTION SPECTROSCOPY STUDY OF THE ELECTRONIC STRUCTURE OF COPPER PHTHALOCYANINE AND ITS FLUOROSUBSTITUTED ANALOG

G. I. Semushkina1, L. N. Mazalov1,2,3, T. V. Basova1, R. V. Gulyaev4
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University
3Novosibirsk State Technical University
4Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: phthalocyanines, X-ray absorption spectroscopy, photoelectron spectroscopy

Abstract >>
An X-ray absorption spectroscopy study of the electronic structure of unsubstituted and hexadecafluoro-substituted copper phthalocyanines is performed. L absorption spectra of the copper atom and K absorption spectra of carbon, nitrogen, and fluorine atoms of unsubstituted and hexadecafluorosubstituted copper phthalocyanine are examined. A comparison of the absorption spectra in one binding energy scale enabled the estimation of contributions of AOs of all atoms of the considered compounds to lower unoccupied molecular orbitals and to determine the sequence of levels, their energies, and the occurrence of the interaction between certain atoms.



7.
COMPARISON OF COMPUTATIONAL STUDIES WITH THE X–RAY CRYSTAL STRUCTURE OF DIRECTLY SYNTHESIZED BIS(D,LAMINOBUTYRIC)COPPER(II) COMPLEX

R. Kumar, S. Obrai
National Institute of Technology, Jalandhar, India
Keywords: copper metal, direct synthesis, Cu(D, L-but)2, ZINDO, INDO, HOMO-LUMO

Abstract >>
The important feature of the present work is that the crystal data are obtained first time for the directly synthesized complex [Cu(D,L-but)2] from pure zero valent metal and butyric acid in water. Further investigation involves the comparison of structural parameters from the XRD data of the title complex [Cu(D,L-but)2] in solid state with the theoretically optimized structure in the gaseous state and its simulated spectra (vibrational and electronic) are generated. The results show that the structural parameters determined by computational studies and crystal structure studies are in good agreement. In the computational calculations, the geometric optimization is carried out using the MM3 method and electronic spectra are calculated using ZINDO, a semi-empirical quantum mechanical method of Scigress explorer 7.7. The theoretical calculations of HOMO-LUMO energies have revealed that the charge transfer interactions occur within the complex. The crystal data for the [Cu(D,L-but)2] complex are: space group P21/c; a = 11.096(5) Å, b = 5.062(4) Å, c = 9.475(3) Å; β = 92.4°; ρcalcd = 1.673 g/cm3; Z = 2.



8.
STRUCTURES AND ENERGIES OF THE TAUTOMERS OF 1–NITROSO1,2,4TRIAZOL5ONE2OXIDE: NEW TRIAZOL5ONENOXIDES

P. Ravi, S.P. Tewari
Advanced Centre of Research in High Energy Materials, University of Hyderabad, Hyderabad, India
Keywords: triazol-5-one-N-oxides, density, heat of explosion, detonation velocity, detonation pressure

Abstract >>
Molecular orbital calculations at the DFT-B3LYP/aug-cc-pVDZ level are performed for the possible tautomers of 1-nitroso-1,2,4-triazol-5-one-2-oxide. We have examined the substitution effects of carbonyl, N-oxide, and nitroso groups by comparing the calculated geometries, relative energies, and electrostatic potentials of model molecules. The optimized structures, vibrational frequencies, and thermodynamic values for triazolone-N-oxides are obtained in the ground state. The results show that 1H, 4H tautomers are most stable. Detonation velocity and detonation pressure are evaluated by the Kamlet-Jacob equations based on the predicted density and the calculated heat of explosion. The explosive properties of the designed compounds seem to be promising compared with those of 1,3,5-trinitroperhydro-1,3,5-triazine (D 8.75 km/s, P 34.70 GPa), octahydro-1,3,5,7-tetrnitro-1,3,5,7-tetrazocine (D 9.10 km/s, P 39.3 GPa), and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (D 9.20 km/s, P 42.0 GPa).



9.
MOLECULAR MOBILITY AND THE STRUCTURE OF POLAR LIQUIDS

M. N. Rodnikova1, F. M. Samigullin2, I. A. Solonina1, D. A. Sirotkin1
1Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
2National Research Technological University, Kazan, Russia
Keywords: self-diffusion coefficients, spatial network of hydrogen bonds, diamines, diols, alkanolamines, dimethylformamide, dimethyl sulfoxide, propylene carbonate

Abstract >>
Self-diffusion coefficients of different classes of polar solvents are measured by the proton spin echo method in the temperature range of 288-318 K. In the same temperature range viscosities and dielectric relaxation times of the liquids under study are measured or taken from the literature and the activation energies of self-diffusion processes, viscous flow, and dielectric relaxation are calculated. The results obtained are compared with the literature data on structural relaxation times in the studied solvents and the conclusion is drawn about the role of the spatial hydrogen bond network in the mobility of molecules forming this network.



10.
ANALYSIS OF THE PRESSURE EFFECT ON THE LOCAL COMPOSITION IN A WATER–ALKANOL MIXTURE USING KIRKWOODBUFF INTEGRALS

D. M. Makarov, G. I. Egorov
Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
dmm@isc-ras.ru
Keywords: water-alcohol mixtures, Kirkwood-Buff integrals, local composition, excess pressur

Abstract >>
Kirkwood-Buff integrals are calculated from the thermodynamic data for binary mixtures of water with methanol, ethanol, 1-propanol, and 2-propanol at a temperature of 298.15 K in the pressure range from atmospheric to 100 MPa. The values of local compositions Δnij are calculated which characterize the excess (or deficit) of molecules i around the central molecule j. It is found that the pressure affects destructively the homoassociation in all mixtures studied. In a series MeOH < EtOH < 2-PrOH < 1-PrOH an excess of molecules around the similar type molecules increases in the local environment and the pressure effect on the local composition is enhanced.



11.
RELATIONSHIP BETWEEN VARIOUSLY ASSOCIATED MOLECULES IN THE HF–Et2CO SOLUTION

G. V. Yukhnevich, E. G. Tarakanova
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
Keywords: binary liquid system, IR spectroscopy, hydrogen bond, heteroassociates, hydrogen fluoride, diethyl ketone

Abstract >>
Data on the relationship between the molecules involved in various heteroassociates (HAs) and «free» molecules in the HF-Et2CO binary liquid system (BLS) are obtained by two independent methods: experimental and computational. The first method is applicable in the 0:1-6:1 molar range provided that the IR spectrum of the solvent molecule contains a band whose frequency and intensity can be measured when this molecule passes from the free state to the composition of all Has present in BLS. The second method is based on taking into account the material balance between the free molecules and molecules involved in various HAs of the solvent and HF. This method requires the knowledge of stoichiometric ratios of molecules in HAs and concentrations at which they appear in the solution. It is shown that in HF-Et2CO BLS, starting from the molar fraction of HF of ~0.25, the majority of molecules is involved in the composition of the complexes, and at the molar fraction of HF of ~0.50-0.92 already 90-100% of molecules of the solution form HAs.



12.
STRUCTURAL–THERMODYNAMIC CHARACTERISTICS AND INTERMOLECULAR INTERACTIONS IN MIXTURES OF STRONGLY ASSOCIATED SOLVENTS WITH APROTIC AMIDES

A. M. Zaichikov1, M. A. Krestyaninov2
1Ivanovo State University of Chemistry and Technology, Ivanovo, Russia
2Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: internal pressure, structural-thermodynamic characteristics, intermolecular interactions, binary solutions

Abstract >>
Thermodynamic characteristics of mixtures of aprotic amides with water and organic solvents with hydrogen bond networks are calculated. Within a model approach the specific and non-specific components of the total energy of the intermolecular interaction are determined, based on which the corresponding contributions to the enthalpies of component mixing are calculated. It is found that negative enthalpies of mixing in the mixtures under study are due to non-specific interactions rather than heterocomponent specific ones. It is shown that the difference in the structural-thermodynamic characteristics of aqueous and nonaqueous mixtures of aprotic amides is mainly caused by packing features of solutions and the behavior of hydrogen bond networks of water and organic solvents.



13.
CRYSTAL STRUCTURE OF [Co(NH3)5Cl]2(W10O32)42O

N. V. Kuratieva1,2, S. P. Khranenko1, S. A. Gromilov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Scientific and Educational Complex Nanosystems and Advanced Materials, Novosibirsk, Russia
Keywords: decatungstate, cobalt, complex salt, crystal chemistry, single crystal X-ray diffraction study

Abstract >>
By single crystal X-ray diffraction the crystal structure of the complex salt [Co(NH3)5Cl]2(W10O32)×4H2O is determined and the IR spectrum is interpreted. The crystal chemical analysis of the structure of complex cations and decatungstate anions and their packing in the structure is performed.



14.
STUDY OF THE CRYSTAL STRUCTURE OF BINUCLEAR BORON DIFLUORIDE ACETYLACETONATE

B. V. Bukvetskii1, I. V. Svistunova2, N. A. Gelfand2
1Institute of Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok, Russia
2Far Eastern Federal University, Vladivostok, Russia
Keywords: β-diketonates of boron difluoride, binuclear complexes, disulfides, crystal structure

Abstract >>
The molecular and crystal structure of binuclear boron difluoride acetylacetonate, in which two boron chelate moieties are linked by a disulfide group, is determined. It is found that in the crystalline state, the chelate moieties are non-equivalent. The differences identified stem from the fact that molecules crystallize in pairs: two chelate ring (one from each molecule of the pair) are linked with each other by the stacking interaction. The other chelate rings of the pair do not participate in intermolecular interactions.



15.
CRYSTAL STRUCTURE OF TWO SALTS DERIVED FROM PARATUNGSTATE IN THE [H2W12O42]10– ANION

E. V. Peresypkina1, A. V. Virovets1, S. A. Adonin1, P. A. Abramov1,2, A. V. Rogachev1, P. L. Sinkevich1,2, V. S. Korenev1,2, M. N. Sokolov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: polyoxometallates, paratungstate B, mixed salts, crystal structure

Abstract >>
Novel mixed salts of the paratungstate anion Na2(NH4)8[H2W12O42]×12H2O (1) and Na7.5K2.5[H2W12O42]×22.2H2O (2) are obtained by slow concentration of tungstate solutions and characterized by single crystal X-ray diffraction.



16.
TWO CRYSTAL MODIFICATIONS OF [PdEn(NO2)2]. SYNTHESIS, STRUCTURE, AND THERMAL PROPERTIES

S. P. Khranenko1, N. V. Kuratieva1,2, P. E. Plyusnin1,2, S. A. Gromilov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: palladium, ethylenediamine, complex compounds, single crystal X-ray diffraction study, crystal chemistry, thermal properties

Abstract >>
The crystal structure of two modifications of [PdEn(NO2)2] is determined by single crystal X-ray diffraction. The geometric characteristics of the complexes and the motifs of their mutual arrangement in the structures are compared. The thermal properties in different gaseous atmospheres are studied.



17.
CRYSTAL STRUCTURES OF [MEn2][Pt(NO2)4] (M = Cu, Pd)

S. P. Khranenko1, N. V. Kuratieva1,2, S. A. Gromilov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: palladium, copper, platinum, ethylenediamine, double complex salt, single crystal X-ray diffraction study, crystal chemistry

Abstract >>
By single crystal X-ray diffraction the structures of [CuEn2][Pt(NO2)4] and [PdEn2][Pt(NO2)4] are determined. In the structures, the main structural moieties are identified. It is shown that the structure of [PdEn2][Pt(NO2)4] can be considered as quasi-one-dimensional: in the Y axis direction, the stacks of alternating complex cations and anions locate.



18.
STRUCTURE, SYNTHESIS, AND THERMAL PROPERTIES OF trans-[Ru(NO)(NH3)4(SO4)]NO3H2O

A. N. Makhinya1,2, M. A. Ilin1,2, I. A. Baidina1, P. E. Plyusnin1,2, N. I. Alferova1, D. P. Pishchur1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: ruthenium, nitroso complexes, amino complexes, sulfato complexes, synthesis, single crystal X-ray diffraction analysis, thermal analysis

Abstract >>
In treatment of trans-[Ru(NO)(NH3)4(OH)]Cl2 with concentrated sulfuric acid on heating trans-[Ru(NO)(NH3)4(SO4)](HSO4)×H2O (I) is obtained with a yield close to quantitative. In the interaction of the saturated solution of I with a saturated NaNO3 solution a trans -[Ru(NO)(NH3)4(SO4)]NO3×H2O (II) precipitate forms whose structure is determined by single crystal XRD: space group 212121, a = 6.8406(3) Å, b = 12.6581(5) Å, c = 13.3291(5) Å. A monodentately coordinated sulfate ion is in the trans-position to the nitroso group. Compound II is characterized by IR spectroscopy, powder XRD, and diffuse reflectance spectroscopy. The process of its thermolysis is studied; by differential scanning calorimetry the thermal effect of the dehydration reaction occurring on heating to 120°C (ΔH = 58.9 ± 1.5 kJ/mol) is estimated. The final product of the thermolysis of II is a mixture of Ru and RuO2.



19.
STRUCTURE OF [Dy(Phen)(C4H8NCS2)3]3CH2Cl2 SOLVATE. MAGNETIC PROPERTIES AND PHOTOLUMINISCENCE OF [Ln(Phen)(C4H8NCS2)3] (Ln = Sm, Eu, Tb, Dy, Tm) COMPLEXES

Yu. A. Bryleva1, L. A. Glinskaya1, I. V. Korolkov1, A. S. Bogomyakov2, M. I. Rakhmanova1, D. Yu. Naumov1, T. E. Kokina1,3, S. V. Larionov1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Institute International Tomography Center, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
3Novosibirsk State University, Novosibirsk, Russia
Keywords: lanthanides, pyrrolidinedithiocarbamate, Phen, mixed-ligand complex, structure, magnetic properties, photoluminescence

Abstract >>
It is found that diffraction patterns of complexes I–V of the composition [Ln(Phen)(C4H8NCS2)3] (Ln = Sm, Eu, Tb, Dy, and Tm respectively) are similar. Single crystals of [Dy(Phen)(C4H8NCS2)3]·3CH2Cl2 (VI) obtained are. According to the X-ray crystallographic data, in the structure of VI the unit cell contains two crystallographically independent molecules of the [Dy(Phen)(C4H8NCS2)3] complex and six CH2Cl2 molecules. The N2S6 coordination polyhedron of the Dy atom is a distorted square antiprism. In the range of 2300 K the magnetic properties of complexes IV are studied. It is found that complex III passes to the magnetically ordered state; the spontaneous magnetization at 2 K is 24 600 Gcm3/mol. At 300 K compounds IIV exhibit photoluminescence in the visible spectral range. It is found that the photoluminescence intensity of complex I is several times higher than the photoluminescence intensity of complexes IIIV.



20.
CRYSTAL STRUCTURE OF COCRYSTALS 2,4,6,8,10,12–HEXANITRO2,4,6,8,10,12HEXAAZATETRACYCLO[5.5.0.0 5.9.0 3.11]DODECANE WITH 7͖ TRIS1,2,5OXADIAZOLO(3,4B:3',4'D:3,4F) AZEPINE

S. M. Aldoshin1, Z. G. Aliev1, T. K. Goncharov1, Yu. M. Milyokhin2, N. I. Shishov2, A. A. Astratyev3, D. V. Dashko3, A. A. Vasilyeva3, A. I. Stepanov3
1Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Russia
2Federal Center for Dual-Use Technologies Soyuz, Novosibirsk, Russia
3Special Construction-Technological Bureau Tekhnolog, Saint Petersburg, Russia
Keywords: 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane, polycyclic nitroamine, azepine, oxadiazole, 7-tris-1,2,5-oxadiazolo[3,4-b:3',4'-d:3,4-f] azepine, single crystal X-ray diffraction study, crystal and molecular structure

Abstract >>
The crystal structure of the bimolecular crystal of CL–20 with new promising highly energetic compound 7͖ tris1,2,5oxadiazolo[3,4b:3',4'd:3»,4f] azepine is obtained and studied.



21.
TWO MONONUCLEAR MOLYBDENUM(VI) OXO COMPLEXES WITH TRIDENTATE HYDRAZONE LIGANDS: SYNTHESIS, STRUCTURES, AND THERMAL STABILITY

S.-S. Qian1, H.-H. Li2, Y.-N. Li2, Z.-L. You2, H.-L. Zhu1
1Shandong University of Technology, ZiBo 255049, P. R. China
2Liaoning Normal University, Dalian 116029, P. R. China
Keywords: molybdenum complex, hydrazone ligand, crystal structure, X-ray diffraction

Abstract >>
A reaction of [MoO2(acac)2] (where acac = acetylacetonate) with two hydrazone ligands in methanol yields two mononuclear molybdenum(VI) oxo complexes with the general formula [MoO2L(CH3OH)], where L = L1=(4-nitrophenoxy)acetic acid [1-(5-chloro-2-hydroxyphenyl)methylidene]hydrazide (H 2L1) and L = L2=4-dimethylaminobenzoic acid [1-(2-hydroxy-3-methoxyphenyl)methylidene]hydrazide (H2L2). The crystal and molecular structures of the complexes are determined by the single crystal X-ray diffraction method. All of the investigated compounds are further characterized by the elemental analysis, FT-IR spectra, and thermogravimetric analyses. Single crystal X-ray structural studies indicate that hydrazone ligands coordinate to MoO2 cores through enolate oxygen, phenolate oxygen, and azomethine nitrogen atoms. The Mo atoms in both complexes are in octahedral coordination.



22.
YTTRIUM(III) COMPLEX WITH 1,10-PHENANTHROLINE LIGAND: CRYSTAL STRUCTURE AND SPECTROSCOPIC STUDIES

A. Moodi1, M. Khorasani-Motlagh1, M. Noroozifar1, B.O. Patrick2
1University of Sistan & Baluchestan, Zahedan, Iran
2University of British Columbia, Vancouver, Canada
Keywords: yttrium(III) complex, crystal structure, 1, 10-phenanthroline, X-ray diffraction analysis

Abstract >>
YYCl3×6H2O reacts with 1,10-phenanthroline (phen) to yield a complex of 1:2 yttrium:ligand stoichiometry. The yttrium(III) complex is characterized by the elemental analysis, UV-Vis, IR as well as the X-ray diffraction analysis. The crystal of [Y(phen)2Cl(H2O)3]Cl2×H2O obtained from a methanol solution crystallizes in the triclinic system, space group P2, Z = 2, a = 10.3236(4) Å, b = 10.4566(4) Å, c = 12.5270(5) Å, α = 97.354(2)°, β = 108.740(2), γ = 93.458(2), Rint = 0.046. The Y(III) ion is eight-coordinated by four nitrogen, three oxygen atoms and one chlorine atom.



23.
TWO SUPRAMOLECULAR COMPLEXES OF GALLIUM(III) WITH DIFFERENT ADDUCT ION PAIRS CONTAINING PYRIDINE–2,6DICARBOXYLIC ACID: SYNTHESES, CHARACTERIZATION, CRYSTAL STRUCTURES AND COMPUTATIONAL STUDY

J. Soleimannejad1, S. Sheshmani2, M. Solimannejad3, E. Nazarnia4, F. Hosseinabadi4
1University of Tehran, Tehran, Iran
2Islamic Azad University, Shahr-e Rey Branch, Tehran, Iran
3Arak University, Arak, Iran
4University of Ilam, Ilam, Iran
Keywords: gallium(III), pyridine-2,6-dicarboxylic acid, 2,9-dimethyl-1,10-phenanthroline, 4,4'-bipyridine, X-ray structure determination, DFT, supramolecular chemistry

Abstract >>
Two complexes of gallium(III) with adduct ion pair compounds containing pyridine-2,6-dicarboxylic acid and two different Lewis bases are synthesized. The chemical formulae are (dmpH)[Ga(pydc)2]×2H2O, (1) and (bpyH2)1/2(pydcH2)1/2[Ga(pydc)2]×4H2O, (2) where pydc, dmp, and bpy are pyridine-2,6-dicarboxylate, 2,9-dimethyl-1,10-phenanthroline, and 4,4'-bipyridine respectively. The two crystal structures illustrate that the GaIII ion is six-coordinated by two pyridine-2,6-dicarboxylates. Hydrogen bonds as well as other noncovalent interactions such as ion-pairing, C-O⋯π, C-H⋯π, and π⋯π stacking play an important role in the formation of supramolecular systems. Particular attention is given to the molecular geometries and NMR properties of the complexes from the computational point of view. The electronic properties of the complexes are analysed using the parameters derived from the atoms in molecules (AIM) and natural bond orbital (NBO) methodologies at the B3LYP/6-311++G(2d,2p) computational level.



24.
THERMODYNAMIC CHARACTERISTICS, STRUCTURE, AND INTERACTIONS OF L–PROLINE IN AQUEOUS SOLUTIONS OF ALCOHOLS AND UREA

V. P. Korolev, O. A. Antonova, N. L. Smirnova
Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: , , , , , L-, 2-, , calorimetry, enthalpic and heat capacity characteristics, ethylene glycol, glycerin, methanol, L-proline, 2-propanol, urea

Abstract >>
The enthalpies of dissolution of imino acid L–proline in aqueous solutions of methanol, 2propanol, ethylene glycol, glycerin, and urea are measured by the calorimetric method at 313.15 K. Enthalpic parameters of the interaction of Lproline with nonaqueous components are calculated and compared with the data at 298.15 K. It is found that the sign of the heat capacity parameter of the pair and ternary interactions depends on whether the nonaqueous solvent component is a destroyer or stabilizer of the water structure. Partial molar heat capacities of proline in mixed solvents are obtained by the integral dissolution heat method. Temperature changes in the reduced enthalpy and entropy of the proline solution are determined at an increase in the temperature from 298 K to 313 K. It is shown that there is entropy-enthalpy compensation at temperature changes in the characteristics during dissolution.



25.
CRYSTAL STRUCTURE OF [{Cu(H2O)(en)2}{Cu(en)2}Re6Te8(CN)6]3H2O

Yu. V. Mironov1, O. A. Efremova2, V. E. Fedorov1,3
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Aston University, Birmingham, W Midland, UK
3Novosibirsk State University, Novosibirsk, Russia
Keywords: octahedral cluster, rhenium, chalcocyanide complex, synthesis, crystal structure

Abstract >>
The reaction of Cs4[Re6Te8(CN)6]×2H2O with Cu(en)2Cl2 in water affords crystals of a cluster complex [{Cu(H2O)(en)2}{Cu(en)2}Re6Te8(CN)6]×3H2O. The structure of the compound is determined by single crystal X-ray diffraction (a = 10.8082(4) Å, b = 16.5404(6) Å, c = 24.6480(7) Å, β = 92.696(1)°, V = 4401.5(3) Å3, Z = 4, space group P21/n, R1 = 0.0331, wR2 (all data) = 0.0652). In the complex, cluster [Re6Te8(CN)6]4–anions are linked by Cu2+ cations into zigzag chains through cyanide bridges. The coordination environment of the copper cations is complemented by ethylenediamine molecules. Each of the cluster anions is additionally coordinated by a terminal fragment {Cu(H2O)(en)2}.



26.
ELECTRONIC STRUCTURE AND MOLECULAR PROPERTIES OF [Re6–xOsxSe8Cl6](4x)(x= 03) CLUSTERS: A STUDY BASED ON TIMEDEPENDENT DENSITY FUNCTIONAL THEORY INCLUDING SPINORBIT AND SOLVENT EFFECTS

L. Alvarado-Soto, R. Ramirez-Tagle
Universidad Bernardo OHiggins, General Gana 1780, Santiago, Chile
Keywords: Luminescent, cluster, TTDFT

Abstract >>
Relativistic time-dependent density functional (TDDFT) calculations including spin-orbit interactions via the zero order regular approximation (ZORA) and solvent effects are carried out on the [Re6–xOsxSe8Cl6](4x ) (x = 03) cluster. These calculations indicate that the lowest energy electronic transitions of the MMCT and LMCT type are similar to those observed in strongly luminescent 24electron hexanuclear rhenium chalcogenide clusters [Re6Se8Cl6]4. Thus our calculations predict that [Re6xOsxSe8Cl6](4x) (x = 03) clusters could be luminescent.



27.
CRYSTAL STRUCTURE OF A NEW π-COMPLEX OF AgClO4 WITH 1–ALLYL5(2PYRIDYL)1HTETRAZOLE OF THE COMPOSITION [Ag2(C9H6N5)2](ClO4)2

Yu. I. Slyvka1, N. T. Pokhodylo1, E. A. Goreshnik2, M. G. Myskiv1
1Franko Lviv National University, Lviv, Ukrainian
y_slyvka@franko.lviv.ua
2Jožef Stefan Institute, Ljubljana, Slovenia
Keywords: silver(I), p complex, tetrazolee, crystal structure

Abstract >>
By the AgClO4 interaction with 1allyl-5-(2-Pyridyl)-1H-tetrazolee (1 aPyt) in a methanol solution, an [Ag2(1 aPyt)2](ClO4)2 π-complex is obtained, which is studied using single crystal X-ray diffraction.



28.
CRYSTAL AND MOLECULAR STRUCTURE OF 1–(3AMMONIOPROPYL)SILATRANE CHLORIDE

M. G. Voronkov1, . A. Zelbst2, V. S. Fundamensky3, V. V. Gurzhiy3, Yu. I. Bolgova1, O. M. Trofimova1
1Favorsky Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
2East Siberian State Academy of Education, Irkutsk, Russia
3Saint-Petersburg State Institute of Technology, Saint-Petersburg, Russia
Keywords: 1-(3-ammoniopropyl)silatrane chloride, molecular structure, single crystal X-ray diffraction study

Abstract >>
By single crystal X-ray diffraction the crystal and molecular structure of 1-(3-ammoniopropyl)silatrane chloride (I) is determined. One of three cations in the asymmetric unit of the crystal of I differs from the other two by the length of the coordination N ® Si bond. The opposite electronic effects in two geometrically similar cations are transferred inductively through a three-carbon chain.



29.
CRYSTAL STRUCTURE AND MAGNETIC PROPERTIES OF HYBRID MATERIALS SELF–ASSEMBLY FROM TETRA(ISOTHIOCYANATE)COBALT(II) ANION AND TRISUBSTITUTED BENZYLTRIPHENYLPHOSPHINIUM

S.-L. Dai, Z.-P. Cheng, R.-K. Huang, Q.-Y. Guan, Y.-J. Liang, W.-Q. Huang, J.-R. Zhou, C.-L. Ni
South China Agricultural University, Guangzhou, P. R. China
Keywords: tetra(isothiocyanate)cobalt(II) anion, substituted benzyl triphenylphosphinium, crystal structure, magnetic properties

Abstract >>
A new hybrid material [BiF4BrBzTPP]2[Co(NCS)4] (1) (BiF4BrBzTPP+ = 2,6-bisfluoro-4-bromobenzyltriphenylphosphinium, NCS = isothiocyanate) is synthesized and characterized by elemental analyses, IR, UV spectra, ESIMS, molar conductivity, single crystal X-ray diffraction and magnetic susceptibility measurements. Compound 1 crystallizes in the monoclinic space group C2/ c with a = 15.272(2) Å, b = 24.779(3) Å, c = 14.482(2) Å, β = 101.037(2), V = 5378.9(12) Å3, Z = 4. The compound comprises two cations and one anion which exhibits a distorted tetrahedral coordination geometry. The short F⋯F, C⋯Br and N⋯Br interactions and CH⋯S hydrogen bonds consolidate the stacking of the molecules. Magnetic susceptibility measurements in the temperature range 2300 K show that 1 exhibits weak antiferromagnetic coupling behavior.



30.
CRYSTAL STRUCTURE AND THERMAL STABILITY OF A μ1,1–(OMe)BRIDGED DIMERIC SCHIFF BASE IRON(III) COMPLEX

S.-S. Qian1, X. Wang2, Z.-L. You2, H.-L. Zhu1
1Shandong University of Technology, ZiBo, P. R. China
2Liaoning Normal University, Dalian, P. R. China
Keywords: Schiff base, iron complex, dimeric complex, crystal structure, thermal stability

Abstract >>
A new μ1,1–OMebridged dimeric iron(III) complex, [Fe2L 21,1OMe)2(NCS)2], where L is the deprotonated form of 2-[(2-ethylaminoethylimino)methyl]-5-methoxyphenol, has been prepared and structural characterized by elemental analysis, IR spectrum, and single crystal X-ray crystallography. The complex crystallizes in the monoclinic space group P21/c, with unit cell dimensions a = 10.156(1) Å, b = 11.972(1) Å, c = 14.256(2) Å, β = 102.643(3)°, V = 1691.3(3) Å3, Z = 2, R1 = 0.0394, and wR2 = 0.0922. Each Fe atom in the complex is in an octahedral coordination. The Fe⋯Fe distance is 3.102(1) Å. The thermal stability of the complex was studied.



31.
CRYSTAL STRUCTURE OF 1–(DIPHENYLMETHYLENE)2(THIAZOLO[4,5b]PYRIDIN2YL)HYDRAZINE

S.B. Miao1,2, B.M. Ji2, L. Zhou1
1Northwest A&F University, Yangling, P. R. China
2Luoyang Normal University, Luoyang, P. R. China
Keywords: 1-(diphenylmethylene)-2-(thiazolo[4,5-b]pyridin-2-yl)hydrazine, synthesis, crystal structure, N-HN hydrogen bond

Abstract >>
The 1-(diphenylmethylene)-2-(thiazolo[4,5-b]pyridin-2-yl)hydrazine compound (IV) is synthesized based on 3-amion-2-chloropyridine precursor and characterized by single crystal X-ray diffraction. The structural analysis reveals that compound IV belongs to the monoclinic system, space group P21/c, a = 11.869(5) Å, b = 13.155(6) Å, c = 10.970(5) Å, β = 102.431(5)°, V = 1672.6(12) Å3, Z = 4. In the crystal structure, the molecular species are linked by intermolecular N-H…N hydrogen bonds into one-dimensional chains.