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Journal of Structural Chemistry

2013 year, number 3

1.
͖ INTERACTION IN PHENANTHRENE: ATTRACTION OR REPULSION?

A. V. Vashchenko, T. N. Borodina
A. E. Favorsky Irkutsk Institute of Chemistry Siberian Division Russian Academy of Sciences, Irkutsk
sasha@irioch.irk.ru
Keywords: phenanthrene, anthracene, QTAIM, EDA, HH interaction

Abstract >>
By the example of the structure of phenanthrene the character of the HH interaction is studied by non-empirical quantum chemical methods. The calculations performed confirm Baders conclusions about the attractive character of the HH interaction, which were made based on the QTAIM analysis, and disprove the repulsive character of the above interaction, which was derived from the EDA procedure.



2.
A QUANTUM CHEMICAL STUDY OF ALKOXY DERIVATIVES OF THREE-COORDINATE ALUMINUM

N. V. Alekseev
Institute of Chemistry and Technology of Organoelement Compounds, Moscow
nalekseev1@rambler.ru
Keywords: alumoxanes, quantum chemistry, NBO method, AIM method

Abstract >>
DFT and HF methods using the PC GAMESS-Firefly program are employed to calculate the spatial and electronic structures of molecules: alkoxy derivatives of aluminum. By NBO and AIM methods the main characteristics of AlO, CO, and AlX bonds in these molecules are determined. It is shown that Al and atoms interact with each other as atoms with closed shells. The іO bonds are close to covalent, whereas the AlX bonds are the intermediate type bonds.



3.
STRUCTURE OF PROTON DISOLVATES FORMED IN THE ACID HYDROLYSIS OF ETHYL FORMATE AND METHYL ACETATE

E. G. Tarakanova, G. V. Yukhnevich
N. S. Kurnakov Institute of General and Inorganic Chemistry Russian Academy of Sciences, Moscow
egtar@igic.ras.ru
Keywords: hydrogen bond, proton affinity, proton disolvate, quantum chemical calculation, ethyl formate, methyl acetate, methyl formate

Abstract >>
By the density functional method (B3LYP/6-31++G(d,p)) optimal structures of proton hetero and homo disolvates involving water molecules, ethyl formate, methyl acetate and products of their hydrolysis are calculated. The data on the structure of these ions and the strength of their H bonds are analyzed together with the results of a similar calculation previously performed for methyl formate. It is shown that in proton solvation by two molecules present in the solution during the hydrolysis of ethyl formate, methyl acetate, and methyl formate stable (X⋯H⋯X)+ or (X⋯H⋯Y)+ particles form. Structural and energy parameters of their O⋯H⋯O bridges obey the same regularities and are mainly determined by a difference in the proton affinity of X and Y molecules. Calculation results are compared to the data of a number of experimental studies of the acid hydrolysis of esters.



4.
INVESTIGATION OF CORRELATION BETWEEN IMPACT SENSITIVITIES AND BOND DISSOCIATION ENERGIES IN BENZENOID NITRO COMPOUNDS

X.-H. Li1,2, D.-F. Han3, X.-Z. Zhang4
1College of Physics and Engineering, Henan University of Science and Technology, Luoyang, China
lorna639@126.com
2Luoyang Key Laboratory of Photoelectric Functional Materials, Henan University of Science and Technology
3Mathematics and Physics Department, Luoyang Institute of Science and Technology, Luoyang, China
4College of Physics and Information Engineering, Henan Normal University, Xinxiang, China
Keywords: density functional theory, bond dissociation energies (BDEs), benzenoid nitro molecules, impact sensitivity

Abstract >>
The geometries of ten benzenoid energetic materials are fully optimized by employing B3LYP and B3P86 methods with the 6-31G** basis set. Bond dissociation energies (BDEs) for the removal of the NO2 group in benzenoid molecules are calculated at the same level. The calculation results show that the insertion of an electron withdrawing group increases the stability of the molecules, while the insertion of an electron donating group reduces the stability of the molecules. In addition, the relationship between the impact sensitivities and the weakest BDE values is examined. There exists a good linear correlation between the impact sensitivity and the ratio of the BDE value to the molecular total energy.



5.
IDENTIFICATION OF ORGANIC REACTION PRODUCTS IN THE ABSENCE OF ADDITIVITY OF CHROMATOGRAPHIC RETENTION INDICES. CHLORO DERIVATIVES OF METHYL-tret-BUTYL KETONE

I. G. Zenkevich, E. V. Eliseenkov, A. N. Kasatochkin
Faculty of Chemistry St. Petersburg State University, St. Petersburg
izenkevich@mail15.com
Keywords: methyl-tert-butyl ketone, chloro derivatives, chromato-mass-spectrometric identification, etention indices, estimation by additive schemes, deviations from additivity

Abstract >>
As a result of a joint interpretation of mass spectra and gas chromatographic retention indices more than ten products of free radical chlorination of methyl-tert-butyl ketone are identified. They contain from one to six chlorine atoms in the molecule and were not previously characterized either by mass spectrometric or chromatographic reference data. It is found that retention index increments corresponding to a gradual increase in the number of chlorine atoms in the molecule per unit are non-additive and vary in wide ranges (from 53 i.u. to 219 i.u.), which does not hinder the use of separate elements of additive schemes for the estimation of the indices of products of such non-regioselective reactions.



6.
ELECTRONIC STRUCTURE OF OCTAVINYLAND OCTAPHENYLSILSESQUIOXANE FROM XPS AND DFT DATA

I. S. Osmushko, V. I. Vovna, V. A. Yashin, V. V. Korochentsev, M. V. Tutov, N. P. Shapkin
Far Eastern Federal University, Vladivostok
vovna@vido.dvgu.r
Keywords: polyhedral siloxanes, XPS, DFT, electronic structure

Abstract >>
X-ray photoelectron spectroscopy (XPS) and density functional theory are employed to study the electronic structure of octasilsesquioxanes (RSiO1.5)8 with vinyl and phenyl terminal groups. Quantitative compositions determined from the XPS data are close to those estimated by empirical formulas. Narrow spectral lines corresponding to ionization from C1s core levels indicate similar chemical states of carbon atoms for both compounds. Experimental data are confirmed by close calculated values of effective charges on carbon atoms when polarization functions are included in the basis set and also by small energy ranges of core level electrons. The valence spectral region is interpreted based on the calculated energy values of electronic levels with regard to the density of states and ionization cross-sections.



7.
A ZWITTERIONIC MONOALKYLATED DERIVATIVE OF [Pt2(-S)2(PPh3)4] FROM 1,3-PROPANESULTONE

O.T. Ujam, W. Henderson, B.K. Nicholson
Department of Chemistry, University of Waikato, Hamilton, New Zealand
w.henderson@waikato.ac.nz
Keywords: platinum complex, alkylation reaction, zwitterions, thiolate ligand, X-ray crystal structure

Abstract >>
Reaction of dinuclear platinum(II) sulfido complex [Pt2(µ-S)2(PPh3)4] with 1,3-propanesultone gives the novel zwitterionic monoalkylated thiolate complex [Pt2(-S){-S(CH2)3SO3}×(PPh3)4], which was characterized by NMR spectroscopy, electrospray ionisation mass spectrometry, and a single crystal X-ray structure determination. Crystals are monoclinic, space group P2(1)/ c with unit cell dimensions a = 16.8957(3) Å, b = 15.5031(3) Å, c = 28.0121(5) Å, β = 99.780(1)°, for Z = 4.



8.
THERMODYNAMIC AND STRUCTURAL PROPERTIES OF AQUEOUS LINEAR DIOL SOLUTIONS

A. M. Zaichikov, S. V. Makarov
Ivanovo State University of Chemistry and Technology, Ivanovo
zam@fromru.com
Keywords: internal pressure, intermolecular interactions, thermodynamic and structural properties of aqueous nonelectrolyte solutions, water, linear diols

Abstract >>
Thermodynamic characteristics of aqueous linear diol solutions are calculated. These data are used to identify regularities in the variations of the structural properties of the mixtures being studied. The correlation between the entropy and enthalpy characteristics of waterdiol systems with excess packing coefficients is evidence that the structural and energy properties of aqueous linear diol solutions are determined by universal interactions. The form of the concentration dependences of the solvation enthalpies and entropies of noble gases in waterlinear diols mixtures is determined by the reorganization component and is attributed to the destruction of the H bond network of water, which results in the formation of the most densely packed solutions in the medium range of compositions.



9.
VOLUMETRIC PROPERTIES, STRUCTURAL EFFECTS, AND HYDRATION OF AMINO ACIDS IN AQUEOUS SALT SOLUTIONS

V. P. Korolev
G. A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo
korolev@isuct.ru
Keywords: partial volume, amino acid, aqueous salt solutions, group contributions, hydration numbers

Abstract >>
The dependence of the standard partial volumes of glycine, a-alanine, and serine on the ionic strength of aqueous sodium chloride and sulfate solutions is modeled by the extended Masson equation: V0 = Vw0 + AI0,5 + BI. The error of less than 0.2 cm3/mol is a result of using five values of the and parameters: the two values of are determined by the type of salt and the three values of by the type of amino acid. A new variation of the additive-group approach is proposed for ΔV0 = V0 - Vw0. The partial volumes of the 3 group (a-alanine) and the 2 group (serine) are found not to depend on the salt concentration. The partial volume of the 2 group of glycine grows with concentration. The structural characteristics of the hydrated complexes of the NH3+ and COO- groups are calculated: the hydration numbers, the molar volumes of water inside and outside the hydration sphere, and the intrinsic volume of NH3+ in COO- in solution. Given the same ionic strength, the aqueous sodium sulfate solution produces a somewhat stronger dehydration of the charged groups.



10.
CRYSTAL STRUCTURE OF MONOCLINIC MODIFICATIONS OF ZIRCONIUM AND HAFNIUM TETRAFLUORIDE TRIHYDRATES

R. L. Davidovich, M. A. Pushilin, V. B. Logvinova, A. V. Gerasimenko
Institute of Chemistry, Far Eastern Division, Russian Academy of Sciences, Vladivostok
davidovich@ich.dvo.ru
Keywords: synthesis, zirconium and hafnium tetrafluorides, X-ray crystallographic analysis, crystal structure, hydrogen bonds

Abstract >>
The monoclinic modification of ZrF4×3H2O, isostructural to HfF4×3H2O, is synthesized and structurally studied for the first time. Unlike the triclinic modification of ZrF4×3H2O with a dimeric structure, the synthesized compound has a polymer structure formed from infinite chains composed of ZrF6(H2O)2 groups sharing F…F edges. The crystal structure of HfF4×3H2O, previously determined by the photo method, is refined. The refined data on the geometric characteristics of the coordination polyhedron of the Hf atom and the system of hydrogen bonds in the structure are obtained.



11.
CRYSTAL STRUCTURE OF THE N,N',N"-TRIPHENYLGUANIDINIUM-bis-[h5-π-(3)-DICARBOLLIDE]Ni(III) COMPLEX

T. M. Polyanskaya, M. K. Drozdova, V. V. Volkov
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division Russian Academy of Sciences, Novosibirsk
polyan@niic.nsc.ru
Keywords: low-temperature single crystal XRD, crystal structure, triphenylguanidinium, bis(dicarbollide)nickel, intermolecular interactions

Abstract >>
Single crystals of a new compound containing triphenylguanidinium and bis(dicarbollide)nickel(III) [C(NHC6H5)3][Ni(B9C2H11) 2] are obtained and analyzed by LOW-TEMPERATURE. Crystallographic data are: C23H40B18N3Ni, M = 611.87, monoclinic system, space group P21/, unit cell parameters: a = 21.9085(5) Å, b = 19.9294(4) Å, c = 14.8721(4) Å, β = 91.4033(9)°, V = 6491,5(4) Å3, Z = 8, dx = 1.252 g/cm3, T = 100 K, F(000) = 2536, μ = 0.621 mm–1. The structure was solved by direct and Fourier methods and refined by the full matrix least squares technique in the anisotropic/isotropic (for H atoms) approximation up to the final factor R1 = 0.053 for 10429 Ihkl ≥ 2σI (Bruker X8 APEX diffractometer, MoKα radiation). It contains two independent [C(NHC6H5)3]+ cations with different conformations and two [Ni(B9C2H11)2] anions with the same transoid conformation. Three types of weak intermolecular interactions are found: NHδ+δHB; CH⋯π between the H(C) atoms of cluster anions and delocalized π systems of Ph rings of cations; π⋯π interactions of Ph rings of cation 2 with each other.



12.
CADMIUM(II) COMPLEX WITH (1'H-[2,2']BIIMIDAZOLY-1-YL)-ACETIC ACID: SYNTHESIS, CRYSTAL STRUCTURE, AND LUMINESCENCE

J. Wang, J.-Q. Tao, X.-J. Xu, C.-Y. Tan
Department of Chemistry, Yancheng Teachers' College, Yancheng, Jiangsu, P.R. China
wjyctu@gmail.com
Keywords: Cd(II) complex, crystal structure, hydrogen bonding, CO…π interaction, photoluminescence

Abstract >>
A new cadmium(II) complex with (1'H-[2,2']Biimidazoly-1-yl)-acetic acid (HBDAC) [Cd(BDAC)2(H2O)2]×H2O is synthesized and structurally characterized, which crystallizes in the monoclinic system, space group P21/c , a = 8.465(3) Å, b = 14.164(5) Å, c = 11.294(3) Å, α = 90°, β = 127.405(17), γ = 90, Z = 2. The [Cd(BDAC)2(H2O)2]H2O units are further bridged by O—HO, NHO, CHO hydrogen bonds, ππ stacking and COπ interactions, generating a three-dimensional supramolecular structure. In addition, luminescence measurements reveal that complex 1 exhibits strong fluorescent emission in the solid state at room temperature.



13.
MOLECULAR AND CRYSTAL STRUCTURE OF AMINO-SUBSTITUTED NITRONYL NITROXIDE AND ITS DERIVATIVES

E. V. Tretyakov, G. V. Romanenko, S. E. Tolstikov, V. I. Ovcharenko
International Tomography Center, Siberian Division, Novosibirsk
romanenko@tomo.nsc.ru
Keywords: nitroxides, crystal structure

Abstract >>
Molecular and crystal structures are determined for amino-substituted nitronyl nitroxide 1, the products of its subsequent oxidation, acylation, and reduction: zwitter-ions 3a, 3b and salts K(4b) and K2(4b)(CF3CO2).



14.
CRYSTAL STRUCTURE OF POTASSIUM 2-THIOBARBITURATE

N. N. Golovnev1, M. S. Molokeev2, M. Yu. Belash3
1Siberian Federal University, Krasnoyarsk
ngolovnev@sfu-kras.ru
2L. V. Kirensky Institute of Physics, Siberian Division, Russian Academy of Sciences, Krasnoyarsk
3Institute of Chemistry and Chemical Technology, Siberian Division, Russian Academy of Sciences, Krasnoyarsk
Keywords: crystal structure, potassium thiobarbiturate, hydrogen bonds, ππ interaction

Abstract >>
The crystal and molecular structure of potassium thiobarbiturate C4H3KN2O2S (C4H4N2O2S–2-thiobarbituric acid, H2TBA) is determined. Crystallographic data for KHTBA are as follows: a = 11.2317(17) Å, b = 3.8687(6) Å, c = 14.557(2) Å, β = 97.448(4)°, V = 627.18(17) Å3, space group P2/c , Z = 4. Each potassium ion is linked with four oxygen atoms and two S atoms forming a distorted octahedron. NH⋯O and CH⋯S hydrogen bonds form a branched three-dimensional network. The structure is also stabilized by the ππ interaction of heterocyclic HTBA ions.



15.
A NEW Zn(II) COMPLEX OF UNUSUAL UNIDENTATE COORDINATION OF 4,4'-BIPYRIDINE, A NEW PRECURSOR FOR THE PREPARATION OF ZINC(II) OXIDE NANOPARTICLES

L. Dolatyari1, P. Seddigi2, A. Ramazani1, M.G. Amiri3, A. Morsali3
1Department of Chemistry, Zanjan Branch, Islamic Azad University, P O Box 49195-467, Zanjan, Islamic Republic of Iran
liladolatyari13510@yahoo.com
2Department of Chemistry, Payame Noor University, 19395-4697 Tehran, Islamic Republic of Iran
3Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P O Box 14155-4838 Tehran, Islamic Republic of Iran
morsali_a@modares.ac.ir
Keywords: zinc(II), 4,4'-bipyridine, coordination polymer, fluorescence, nanoparticles

Abstract >>
A 4,4'-bipyridine Zn(II) complex [Zn(4,4'-bipy)2(H2O)4](ClO4)2×4(4,4'-bipy) is synthesized, characterized by elemental analysis, IR, 1H NMR, 13C NMR spectroscopy, and studied by X-ray crystallography. The compound forms monomeric units as a result of unusual unidentate coordination of 4,4'-bipy ligands. The thermal stability of the compound is studied by thermal analyses. Furthermore, the complex is luminescent with emission maxima at 329 nm in the methanol solvent. Different sizes of zinc(II) oxide nanoparticles are prepared by calcination of the [Zn(4,4'-bipy)2(H2O)4](ClO4)2×4(4,4'-bipy) compound at two different temperatures. These nanostructures are characterized by X-ray powder diffraction and scanning electron microscopy.



16.
CRYSTAL STRUCTURE OF {AQUAIMIDAZOLE-[2-(2-carbamoylhydrazone)-propionato]}COPPER(II) NITRATE

Yu. M. Chumakov1, V. I. Tsapkov2, E. Jeanneau3, A. P. Gulea2
1Institute of Applied Physics, Academy of Sciences of Moldov, Chisinau
2Moldova State University, Chisinau
vtsapkov@gmail.com
3Claude Bernard University, Lyon, France
Keywords: 3d metal complexes, X-ray crystallographic analysis, semicarbazone of pyruvic acid, imidazole

Abstract >>
The crystal structure of {aquaimidazole[2-(2-carbamoylhydrazone)-propionato]}copper(II) nitrate [Cu(L)Im(H2O)]NO3 (I), where HL is the semicarbazone of pyruvic acid, Im is imidazole, is dtermined. The crystal structure of I contains two independent complexes I and I in which copper atoms coordinate once deprotonated tridentate L, imidazole, and water molecules. Outer spheres of the complexes contain nitrate ions. In the compounds studied the coordination polyhedron of the copper atom is a distorted tetragonal pyramid. Its base is composed of carboxyl and carbamide oxygen atoms, azomethine nitrogen of monodeprotonated HL molecules, and the imidazole nitrogen atom. In the crystal, nitrate ions and imidazole molecules link the complexes via hydrogen bonds into 2D networks parallel to the (010) plane. These networks in turn are in pairs arranged into layers along the [010] direction due to hydrogen bonds between water molecules and oxygen atoms of nitrate ions, and also by water molecules and O3 atoms of the neighboring 2D networks. In the crystal, the π–π stacking interaction is observed between the imidazole rings from different layers and there is also a NO⋯Cg (π ring) interaction inside the layers.



17.
CRYSTAL STRUCTURES OF new ISOSTRUCTURAL OXOVANADIUM(V) COMPLEXES WITH HYDRAZONE LIGANDS

J. Yu
College of Biological and Chemical Sciences Engineering, Jiaxing University, Jiaxing P. R. China
JXXYYuJ@yahoo.cn
Keywords: oxovanadium complex, synthesis, crystal structure, hydrazone

Abstract >>
Two new isostructural methoxide-bridged dimeric oxovanadium(V) complexes [VO(L1)(OMe)]2 (1) and [VO(L2)(OMe)]2 (2), where L1 and L2 are the deprotonated forms of 3-bromo- N'-[1-(2-hydroxyphenyl)ethylidene]benzohydrazide (H2L1) and 3-chloro-N '-[1-(2-hydroxyphenyl)ethylidene]benzohydrazide (H2L2) respectively, are synthesized and characterized by elemental analyses, IR spectra, and single crystal X-ray determination. Both crystals crystallize in the triclinic space group P-1. For 1, a = 7.5237(15) Å, b = 10.846(3) Å, c = 11.195(3) Å, α = 84.143(3)°, β = 72.244(3), γ = 77.869(3), V = 849.9(4) Å3, Z = 1, R1 = 0.0634, wR2 = 0.1373. For 2, a = 7.493(2) Å, b = 10.740(3) Å, c = 11.109(3) Å, α = 84.569(2), β = 71.783(2), γ = 79.822(2), V = 835.0(4) Å3, Z = 1, R1 = 0.0511, wR2 = 0.1076. Each V atom in the complexes is octahedrally coordinated.



18.
ZINC(II) COMPLEXES WITH THE TETRADENTATE SCHIFF BASE LIGAND N,N'-BIS(1-PYRIDIN-2-YL-ETHYLIDENE)PROPANE-1,3-DIAMINE: SYNTHESIS AND CRYSTAL STRUCTURES

H.-Q. Xie, Y. Xiong, Y.-L. Dang
Chemistry and Pharmaceutical Engineering College, Nanyang Normal University, Nanyang, P.R. China
xiehaiquan0001@163.com
Keywords: zinc(II), Schiff base, synthesis, crystal structure

Abstract >>
Two new zinc(II) complexes [ZnL(N 3)]×BF 4 (1) and [ZnBrL]×BF 4 (2), derived from the tetradentate Schiff base ligand N,N'-bis(1-pyridin-2-yl-ethylidene)propane-1,3-diamine (L), are prepared and characterized by physicochemical methods and single crystal X-ray crystallography. The crystal of (1) is triclinic: space group P-1, a = 8.593(1) Å, b = 8.752(1) Å, c = 13.393(2) Å, α = 97.153(1)°, β = 93.046(1), γ = 91.577(1), V = 997.4(2) Å3, Z = 2. The crystal of (2) is triclinic: space group P-1, a = 8.351(1) Å, b = 8.956(1) Å, c = 13.139(2) Å, α = 92.716(1), β = 94.241(2), γ = 95.016(1), V = 974.8(2) Å 3, Z = 2. The geometries of the penta-coordinated zinc atoms in both complexes are intermediate between the square pyramid and the trigonal bipyramid having the Addison parameters of 0.39 and 0.47 respectively. The syntheses of the complexes show distinct preference for the anions in the order Br >N3> CH3COO.



19.
CRYSTAL STRUCTURE OF BIS-ISONICOTINOYL HYDRAZONE OF 2,5-DIFORMYLPYRROLE

L. D. Popov1, S. I. Levchenkov2, I. N. Shcherbakov1, M. A. Kiskin3, N. E. Borisova4, A. A. Tsaturyan1, V. A. Kogan1
1Southern Federal University, Rostov-on-Don
physchem@yandex.ru
2Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don
3N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow
4Moscow State University, Moscow
Keywords: hydrazones, single crystal X-ray diffraction study, hydrogen bond, density functional theory

Abstract >>
bis-Isonicotinoyl hydrazone of 2,5-diformylpyrrole existing in the crystal in the form of a tetrahydrate of the hydrazone tautomeric form is synthesized and its structure is described. In the crystal, an infinite three-dimensional network of hydrogen bonds is formed by hydrazone molecules. The neighboring hydrazone molecules are bonded by intermolecular π stacking interactions. A quantum chemical calculation of the geometry and total energy of possible tautomers in vacuum and an aqueous solution is performed.



20.
STRUCTURAL ORGANIZATION OF DITHIOCARBAMATE HETEROPOLYNUCLEAR GOLD(III)-CADMIUM COMPLEXES FROM X-RAY CRYSTALLOGRAPHY AND 113Cd MAS NMR SPECTROSCOPY DATA

O. V. Loseva1, T. A. Rodina2, A. V. Ivanov1, A. V. Gerasimenko3, O. N. Antsutkin4,5
1Institute of Geology and Nature Management, Far Eastern Division, Blagoveshchensk, Russia
losevao@rambler.ru
2Amur State University, Blagoveshchensk, Russia
t-rodina@yandex.ru
3Institute of Chemistry, Far Eastern Division, Vladivostok, Russia
gerasimenko@ich.dvo.ru
4Warwick University, Lule, Sweden
olan@ltu.se
5University of Technology
Keywords: cadmium dialkyldithiocarbamates with chemisorbent properties, forms of binding of gold from solutions, heteropolynuclear gold(III)cadmium complexes, crystal and supramolecular structure, single-crystal XRD, 113Cd MAS NMR, 113Cd chemical shift anisotropy

Abstract >>
We study the interaction of dialkyl substituted and cyclic cadmium dithiocarbamates with [AuCl4] anions in 2M HCl medium. The state of the chemisorbents upon contact with AuCl3 solutions is controlled by 113Cd MAS NMR spectroscopy. The result of the heterogeneous reactions involving chemisorption binding of gold(III) from the solutions and partial ion exchange is the formation of heteropolynuclear gold(III)cadmium complexes. The crystal and molecular structure of the acetone-solvated form of polymeric bis-(N,N-diethyldithiocarbamato-S,S') gold(III) hexachlorodicadmate is identified by single-crystal XRD. The main structural moieties of the compound are complex [Au{S2CN(C2H5)2}2]+ cations and [Cd2Cl6]2 anions. The structural self-organization of the complex at the supramolecular level is attributed to the secondary Au⋯S bonds between neighboring isomeric complex gold(III) cations; the bonding results in the formation of linear polymer ([Au{S2CN(C2H5)2}2]+)n chains, with [Cd2Cl6]2 anions alternating to the right and left of the chains.



21.
CRYSTAL STRUCTURE OF TWO HYDRATE phases of ciprofloxacindi-um TETRACHLORIDOCOBALTATE(II)

A. D. Vasiliev1,2, N. N. Golovnev3
1L. V. Kirensky Institute of Physics, Siberian Division, Russian Academy of Sciences, Krasnoyarsk
2Siberian Federal University
3Siberian Federal University, Krasnoyarsk
ngolovnev@sfu-kras.ru
Keywords: ciprofloxacindi-um tetrachloridocobaltate(II), crystal structure, hydrogen bonds, ππ interaction

Abstract >>
New (C17H20FN3O3)2[CoCl4]2×3H2O (I) and C17H20FN3O3[CoCl4]×H2O (II) compounds, where C17H18FN3O3 is ciprofloxacin (CfH), are synthesized and their crystal structures are determined. Crystallographic data for I: a = 18.441(5) Å, b = 9.030(3) Å, c = 27.551(8) Å, V = 4588(4) Å3, space group Pca21, Z = 4; for II: a = 9.305(3) Å, b = 9.885(3) Å, c = 12.999(4) Å, α = 82.782(4)°, β = 72.954(4), γ = 89.736(4), V = 1133(1) Å3, P–1 space group, Z = 2. Both structures contain CfH32+ ion pairs bonded by the ππ interaction. Additionally, in the crystal of I there is a stacking interaction between the π clouds of aromatic rings and hydrogen atoms of the cyclopropyl group linking the pairs of molecules with each other. The structure of the centrosymmetric crystal of triclinic phase II is also formed from CfH32+ ion pairs bonded by the ππ interaction, which, in this case, are not independent because they are related by the symmetry center. Hydrogen bonds form a branched three-dimensional network linking the CfH32+ and CoCl42 ions and water molecules.



22.
STRUCTURE OF A NEW TRINUCLEAR NICKEL(II) COMPLEX WITH A SALEN-TYPE BISOXIME LIGAND

W.-K. Dong1, Y.-X. Sun1, J. Yao1, L. Wang1, X.-Y. Dong1, X.-H. Gao2
1School of Chemical and Biological Engineering, Lanzhou Jiaotong University, P. R. China
dongwk@126.com
2Lanzhou Petrochemical Research Center, PetroChina, P. R. China
Keywords: salen-type bisoxime ligand, Ni(II) complex, synthesis, crystal structure

Abstract >>
A new trinuclear Ni(II) complex {[NiL(DMF)]2(OAc)2Ni}×2DMF (H2L = 4,4'-dichloro-2,2'-[(1,3-propylene)dioxybis(nitrilomethylidyne)]diphenol) is synthesized and characterized by elemental analyses, IR spectra, UV—Vis spectra and X-ray crystallography. The results show that the Ni(II) complex consists of three Ni(II) ions, two tetradentate (μ-L)2– units, two coordinated μ-acetate ions, two coordinated DMF molecules, and two crystallization DMF molecules. All hexacoordinated Ni(II) ions of the complex have a slightly distorted octahedral geometry. The crystal packing of the Ni(II) complex reveals a notable feature of this structure: the formation of an infinite supramolecular 2D layered structure by virtue of intermolecular CH⋯O hydrogen bonding.



23.
CRYSTAL STRUCTURE OF THE POLYCYCLIC OXIDATION PRODUCT OF 1'-PHTHALAZINYLHYDRAZONE OF 2-FORMYLPYRROLE

L. D. Popov1, S. I. Levchenkov2, I. N. Shcherbakov1, G. G. Aleksandrov3, Yu. P. Tupolova1, V. V. Lukov1, O. I. Askalepova1, V. A. Kogan1
1Faculty of Chemistry, Southern Federal University, Rostov-on-Don
physchem@yandex.ru
2Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don
3N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow
Keywords: hydrazones, single crystal X‑ray diffraction analysis, hydrogen bond, density functional theory

Abstract >>
Phthalazinylhydrazone of 2-formylpyrrole is synthesized, the values of ionization constants are determined, and quantum chemical calculation of the geometry and total energy of possible tautomers is performed. The structure of the cyclic oxidation product of hydrazone 3-(1H-pyrrolyl-2)-[1,2,4]-triazolo(3,4-a)phthalazine existing in the crystal in the form of dimers linked by two hydrogen bonds is described.



24.
STRUCTURE OF A NEW SCHIFF BASE COBALT(III) COMPLEX WITH ANTIBACTERIAL ACTIVITY

C.-H. Dai, F.-L. Mao
Jiangsu Provincial Key Laboratory of Coastal Wetland Bioresources and Environmental Protection, Deparment of Chemistry, Yancheng Normal College, Yancheng, P. R. China
xpzhougroup@163.com
Keywords: schiff base, cobalt(III) complex, synthesis, crystal structure, biological activity

Abstract >>
A new Schiff base cobalt(III) complex with the formula [CoL1L2(N3)]×NO3 (L1 is 2-[1-(2-phenylaminoethylimino)ethyl]phenolate, L2 is N-phenylethane-1,2-diamine) is prepared and characterized by physicochemical methods and single crystal X-ray determination. The complex crystallizes in the triclinic system space group P-1, with a = 8.504(2) Å, b = 14.973(3) Å, c = 20.676(4) Å, α = 100.021(3)°, β = 90.005(3), γ = 103.084(2), V = 2523.0(9) Å3, Z = 4, R1 = 0.0732, and wR2 = 0.1182. Single crystal X-ray diffraction analysis reveals that the complex contains two mononuclear [CoL1L2(N3)]+ cations and two nitrate anions. The Co atom is six-coordinated in an octahedral geometry. The ligands and the cobalt(III) complex are screened in vitro for their antibacterial activity against Bacillus subtillis, Staphylococcus aureus, Escherichia coli, and Pseudomonas aereuguinosa.



25.
DIMEPHOSPHONE ANALOGUES. 3. MOLECULAR AND CRYSTAL STRUCTURE OF DIMEPHOSPHONE PYRIDINOYLHYDRZONES EXHIBITING ANTIPHTHISIC ACTIVITY

E. V. Mironova, B. I. Buzykin, V. N. Nabiullin, I. A. Litvinov, V. F. Mironov
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Kazan
katy@iopc.ru
Keywords: dimephosphone pyridinoylhydrazones, dimephosphone nicotinoylhydrazone, dimephosphone iso-nicotinoylhydrazone, structure of acylhydrazones, geometrical isomers, amide conformers, X-ray crystallography, biological activity, toxicity, antiphthisic activity

Abstract >>
Molecular and crystal structures of dimephosphone nicotinoylhydrazone and dimephosphone iso-nicotinoylhydrazone exhibiting antiphthisic activity are studied. In contrast to aroylhydrazones of arylaldehydes, existing in the crystalline state as a mixture of two amide conformers, the studied hydrazones exist in the crystalline state in the single geometrical form EC=NEN—NZNC().



26.
EPR INVESTIGATION OF THE ORIGIN OF THE MAGNETIC FIELD EFFECT ON THE DIMERIZATION OF ALUMINUM(III) AND GALLIUM(III) PHTHALOCYANINE CHLORIDES IN FILM STRUCTURES

A. S. Berezin, V. A. Nadolinnyi, T. V. Basova
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
spectr@niic.nsc.ru
Keywords: aluminum(III) phthalocyanine, gallium(III) phthalocyanine, spin trap, magnetic moment, EPR

Abstract >>
The origin of the magnetic field effect on the dimerization of aluminum(III) and gallium(III) phthalocyanine chloride films is revealed. The EPR technique is employed to demonstrate that the dimerization of the above coordination compounds occurs via a free radical pathway with the formation of phthalocyanine and OH radicals, thus resulting in the appearance of the magnetic moment in the studied compounds.



27.
CRYSTAL STRUCTURE OF [Pt3S2(P(CH2OH)3)6](PF6)(OH)•H2O

A. V. Anyushin1,2, M. N. Sokolov1,2, A. V. Virovets1, V. P. Fedin1
1A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
caesar@niic.nsc.ru
2Novosibirsk State University
Keywords: platinum complexes, sulfide clusters, water-soluble complexes, crystal structure, hydrogen bonds

Abstract >>
[Pt3S2(P(CH2OH)3)6](PF6)(OH)×H2O (1) is obtained by a reaction of [Pt3S2(P(CH2OH)3)6]Cl2 with NH4PF6. The crystal structure of 1 was determined by a single crystal X-ray diffraction analysis (space group R3c a = 12.0042(2) Å, c = 52.6879(11) Å, V = 6575.2(2), Z = 6, C18H57F6O20P7Pt3S2, dx = 2.385 g/cm3, T = 150 K, R1 = 0.044 for 2123 F0 > 4δ(F) until 2θmax = 63°). The cations contain a {Pt33-S)2}2+ core with nonbonding Pt…Pt distances of 3.1536(6) Å. The Pt atoms are in a square planar environment; the Pt–S and PtP bond lengths are 2.3586(16) Å and 2.260(2) Å respectively.



28.
CRYSTAL STRUCTURE OF 9-(FURAN-2-YL)-4,5,6,7,8,9-HEXAHYDRO-[1,2,3,4]TETRAZOLO[1,5-b]QUINAZOLINE

A. A. Matveeva1, P. V. Reshetov2, A. P. Krivenko1
1N. G. Chernyshevsky Saratov State University, Saratov
annamatveeva2008@yandex.ru
2V. I. Razumovsky Saratov State Medical University, Saratov
Keywords: single crystal X-ray diffraction, crystal structure, 9-(furan-2-yl)-4,5,6,7,8,9-hexahydro[1,2,3,4]tetrazolo[5,1-b]quinazoline

Abstract >>
Single crystal X-ray diffraction is used to determine the crystal structure and conformational features of 9-(furan-2-yl)-4,5,6,7,8,9-hexahydro[1,2,3,4]tetrazolo[5,1-b]quinazoline obtained by three-component cyclocondensation of furfurol, 5-amino-1-1,2,3,4-tetrazole, and cyclohexanone.



29.
CRYSTAL STRUCTURE OF 1-(4-CHLOROPHENYL)-3-{4-[2-(5-ETHYL-PYRIDIN-2-YL)-ETHOXY]-PHENYL}-PROPENONE

M. Kayalvizhi1, G. Vasuki1, K. Ramamurthi2, B. Patel Navin3, R. Patel Hemant3
1Department of Physics, Kunthavai Naachiar Government Arts College (w) Autonomous, Tamilnadu, India
vasuki.arasi@yahoo.com
2Crystal Growth and Thin Film Laboratory, School of Physics, Bharathidasan University, Tamilnadu, India
3Department of Chemistry, Veer Narmad South Gujarat University, Gujarat, India
Keywords: chalcones, propenone, chlorophenyl, pyridine ring

Abstract >>
The title compound C24H22ClNO2 belongs to the orthorhombic system, space group Pca21 with a = 12.1771(10) Å, b = 4.9305(4) Å, c = 34.419(3) Å, α = β = γ = 90°, V = 2066.5(3) Å3, Z = 4, Dc = 1.260 g/cm3, F(000) = 824, R = 0.0402 and wR = 0.1144, S = 1.034, T = 293 K. The compound is a chalcone with 4-chlorophenyl and [(5-ethyl-pyridin-2-yl)-ethoxy]-phenyl substituents bonded at the opposite ends of a propenone group, the biologically active region. The propenone bridge makes dihedral angles of 10.61(23) and 62.75(22) respectively, with 4-chlorophenyl and the [(5-ethyl-pyridin-2-yl)-ethoxy]-phenyl group.



30.
CO-CRYSTAL STRUCTURE OF MIXED MOLECULES OF METHYL 2-(3-CHLORO-4-METHYL-2-OXO-2H-CHROMEN-7-YLOXY)ACETATE AND 2-(2-AMINOPHENYL)BENZOTHIAZOLE

A. A. Al-Amiery1,2, A.A. Al-Temimi2, A. A. H. Kadhum1, Ya. K. Al-Majedy2, R. I. Al-Bayati2, H. A. Aday2, A. B. Mohamad1
1Department of Chemical and Process Engineering, Faculty of Engineering and Built Environment, Universiti of Kebangsaan Malaysia, Bangi, Selangor, 43600, Malaysia
dr.ahmed1975@gmail.com
2Chemistry Division, Applied Science Department, University of Technology, Baghdad, Iraq
Keywords: 2-(2-aminophenyl)benzothiazole, co-crystal, coumarins, methanol, single crystal X-ray

Abstract >>
A co-crystal is obtained in a methanolic solution from methyl 2-(3-chloro-4-methyl-2-oxo-2H-chromen-7-yloxy)acetate and 2-(2-aminophenyl)benzothiazole. In the crystal these molecules are connected via usual NHO and weak CHO H-bonds. The co-crystals are very stable.