Publishing House SB RAS:

Publishing House SB RAS:

Address of the Publishing House SB RAS:
Morskoy pr. 2, 630090 Novosibirsk, Russia



Advanced Search

Journal of Structural Chemistry

2011 year, number 1

1.
A QUANTUM CHEMICAL STUDY OF GERMANIUM- SUBSTITUENT BONDS IN SUBSTITUTED GERMYLENES

N. V. Alekseev1, E. A. Chernyshev2
1 , nalekseev1@rambler.ru
2
Keywords: quantum chemistry, germylenes, AIM method, NBO method
Pages: 7-14

Abstract >>
The spatial and electronic structures of a series of substituted germylene molecules are calculated by DFT and HF methods using the PC GAMESS-Firefly program package. Molecular structures are optimized at the DFT (B3LYP/6-31G(2d,p)) level; wave functions and topological characteristics of the electron density distribution are calculated in the HF/acc-pvtz approximation. By means of NBO and AIM methods, the main characteristics of Ge-X bonds in these molecules are determined. The Ge-X bonds are shown to be the intermediate type bonds. The energies of these bonds are estimated.



2.
A universal solution of the problem of the thermodynamic limit in crystals with coulomb and multipole interactions

E. V. Kholopov
Keywords: crystal lattice, lattice sums, direct summation, Coulomb energy, dipole interaction, quadrupole interaction, Lorentz tensor
Pages: 15-21

Abstract >>
A solution of the problem of conditional convergence is obtained in the calculation of Coulomb and multipole energy contributions within direct summation over the crystal lattice. The values correcting the results of the direct summation are shown to have the universal character described by the Lorentz tensor whose components are determined only by crystal symmetry and the direct summation method.



3.
A Theoretical study of keto-enol isomerism and Internal rotation in the H2Salen molecule, N,N′-ethylene-bis(salicylidenimine) - Schiff Base

V. V. Sliznev1, G. V. Girichev2
1
2
Keywords: Schiff base, H2Salen, structure, keto-enol isomerism, internal rotation, conformers, intramolecular hydrogen bond, hyperconjugation, electron density functional theory
Pages: 22-32

Abstract >>
Geometric parameters, vibrational spectra, and the energies of isomerization of seven keto-enol isomeric forms of the H2Salen molecule (N,N′-ethylene-bis(salicylidenimine)) are calculated using electron density functional theory (DFT/B3LYP) and correlation consistent valence triple-zeta Gaussian basis sets (-pvtz). The isomer with two enol groups (EE1) and C2 symmetry configuration is most energetically favorable. Calculations of the keto-enol equilibrium show that at ≥ 250 K the H2Salen gas phase is a mixture of four conformers (rotamers of the main isomer EE1). The contribution of other isomers does not exceed a few percent. The NBO analysis reveals that the system of π-conjugated bonds involves not only the atoms of the benzene moiety, but also the O, C, and N atoms nearest to the benzene ring. The energy stabilization of the isomer EE1 is shown to be due to the presence of two strong intramolecular NH hydrogen bonds. Intramolecular NH and OH hydrogen bonds are observed in all other isomers. The bathochromic shift of O-H and N-H vibrational frequencies, caused by the effect of hydrogen bonds, is 520-790 cm-1.



4.
A quantum chemical study of self-association of HAlBu AND ClAlBu

E. Y. Pankratyev1, S. L. Khursan2, T. V. Tyumkina3, L. M. Khalilov4
1
2
3
4
Keywords: di-iso-butylaluminum hydride, di-iso-butylaluminum chloride, self-association, equilibrium, quantum chemistry, ab initio and DFT simulation
Pages: 33-40

Abstract >>
The self-association of di-iso-butylaluminum hydride and di-iso-butylaluminum chloride is studied at the level of density functional theory and second order Möller-Plesset perturbation theory. Thermodynamic parameters of the monomeric, dimeric, trimeric, and tetrameric forms of HAlBu and ClAlBu in a range of 203 K to 373 K are calculated. The energy of solvation is taken into account by the COSMO polarized continuum model. Based on the obtained results the equilibrium concentrations of the associated forms of organoaluminum compounds (OACs) are calculated, which agree with the experimental data. So, at room temperature the dimeric or trimeric forms of OACs are dominant in the gas phase and non-polar solvents; the tetrameric form is present, while the concentration of the monomeric form is negligibly low and decreases with decreasing temperature or diluting.



5.
Structure and Stability of Endohedral Complexes 4/2X@(HAlNH)12 (X = N, P, As, C-, Si-)

C.-YU. Zhang1, X. Zhao2, J. Zhang3, B.-Q. Wang4
1 Department of Chemistry and Material Science, Shanxi Normal University
2 Department of Chemistry and Material Science, Shanxi Normal University
3 Department of Chemistry and Material Science, Shanxi Normal University
4 Department of Chemistry and Material Science, Shanxi Normal University
Keywords: density functional theory, endohedral complexes, inclusion energy, quartet state, doublet state
Pages: 41-47

Abstract >>
The structures of a closo-hedral cluster (HAlNH)12 and endohedral complexes 4/2X@(HAlNH)12 (X = N, P, As, C-, Si-) are studied by density functional theory (DFT) at the B3LYP/6-31G(d) level. The geometries, natural bond orbital (NBO), vibrational frequency (ν1), energetic parameters, magnetic shielding constants (σ), and nucleus independent chemical shifts (NICSs) are discussed. It is found that all guest species are minima at the cage center. Inclusion energies (ΔEinc) of all species are negative except those of 4N and 4/2P. In all species, the endohedral quartet states (4X) are energetically less favorable than their doublet states (2X). The calculations predict that caged X states only donate <0.50 e to the cage and preserve their unencapsulated ground states.



6.
comment on the ab initio vibrational analysis of the rotational isomers of acrolein

Y. N. Panchenko1, A. V. Abramenkov2, C. W. Bock3
1
2
3
Keywords: trans- and cis-acrolein, vibrational spectra, ground and lowest excited electronic states, isotopic shifts
Pages: 48-59

Abstract >>
Due to the publication of a number of contradictory assignments of the vibrational wave numbers of rotational isomers of acrolein in the ground electronic state, the analysis of their vibrational spectra is repeated based on the previously calculated scaled ab initio force fields. With the use of the reported results that predicted the force fields of trans-acrolein in the 1(n,π*) and 3(n, π*) states at the CASSCF/cc-pVTZ level, the experimental vibrational bands are analyzed in these excited electronic states based on well-established regularities. It is noted that in the assignment of the calculated vibrational wave numbers of the molecule, the isotopic shifts in the ground and excited electronic states 1(n, π*) and 3(n, π*) are taken into account. The previously considered calculated potential curves of the internal rotation of acrolein in combination with the data on the difference in the enthalpies (ΔH0) of conformers allow a choice to be made in favor of one of the variants of the torsional vibration wave numbers that have been reported in the literature.



7.
A percolation model for carbon nanotube-polymer composites using the Mandelbrot-Given curve

M. Monajjemi1, H. Baheri2, F. Mollaamin3
1 Department of Chemistry Science and Research Branch Islamic Azad University
2 Science and Research Branch Islamic Azad University, h.baheri@gmail.com
3 Department of Chemistry Qom Branch Islamic Azad University
Keywords: percolation theory, fractal, Mandelbrot-Given curve, carbon nanotube composites
Pages: 60-64

Abstract >>
A model is introduced for the conductivity of carbon-nanotube polymer composites based upon percolation theory and fractals. These types of polymer composites have been developed in the recent years, and experimental data on their percolation threshold is available. We constructed a fractal space with the aim of the generalized Mandelbrot-Given curve and used the experimental critical exponent of conductivity to calculate the parameters of such a curve. Finally, the moments of the current distribution function are estimated, and the effect of the critical exponent on this function is investigated.



8.
Gas electron diffraction and quantum chemical Studies of THE Molecular structure of 2-nitrobenzenesulfonic acid

V. M. Petrov1, N. I. Giricheva2, G. V. Girichev3, V. N. Petrova4, S. N. Ivanov5, A. V. Bardina6
1
2
3
4
5
6
Keywords: 2-nitrobenzenesulfonic acid, conformer, molecular structure, gas electron diffraction, quantum chemistry, mass-spectrometry
Pages: 65-73

Abstract >>
A combined gas electron diffraction and quantum chemical (B3LYP/6-311+G**, B3LYP/cc-pVTZ) study of the molecular structure of 2-nitrobenzenesulfonic acid (2-NBSA) is performed. Quantum chemical calculations show that the 2-NBSA molecule has five conformers, and the Gibbs energy of one of them is lower by more than 4.5 kcal/mol than the energy of the other conformers. It is found experimentally that the saturated vapor of 2-NBSA at = 394(5) K contains only the low-energy conformer that has an intramolecular hydrogen bond between the H atom of the hydroxyl group and one of the atoms of the NO2 group. The C-C-S-O() torsion angle determining the position of the S-O() bond is -72(7), while the NO2 group is substantially turned relative to the benzene ring plane (C1-C2-N-O = 40(5)). The following experimental values of the internuclear distances are obtained for this conformer (Å): rh1(C-H)av = 1.07(2), rh1(C-C)av = 1.401(4), rh1(C-S) = 1.767(6), rh1(S=O)av = 1.412(4), rh1(S-O) = 1.560(6), rh1(N-O)av = 1.217(5), rh1(C-N) = 1.461(8), rh1(O-H) = 0.99(3).



9.
A STUDY OF THE HYDROLYSIS OF AND THE STRUCTURE OF INTERMEDIATE HYDROLYSIS PRODUCTS BY 19F AND 91Zr NMR IN THE 9.4 T FIELD

M. A. Fedotov1, A. V. Belyaev2
1
2
Keywords: Zr(IV), fluorides, fluoride complexes, hydrolysis, polycondensation, 19F and 91Zr NMR
Pages: 74-79

Abstract >>
The high-field 19F and 91Zr NMR method is used to study the hydrolysis and polycondensation of hexafluorozirconate in aqueous and water-peroxide solutions. During hydrolysis in aqueous solutions only and F- ions were observed by NMR, however, in the water-peroxide medium, an intermediate product of hydrolysis ( [F5Zr-OO-ZrF5]4- dimer) was detected. The dimer structure is confirmed by 19F and 91Zr NMR. In high fields (19F NMR frequency > 200 MHz), the fluorine exchange between and F- is slow in the 19F NMR scale and has a multisite character.



10.
A Hierarchic structure in zirconium butoxide complexes in n-butanol solutions

V. V. Kanazhevskii1, N. S. Kotsarenko2, V. N. Kolomiichuk3, D. I. Kochubey4
1
2
3
4
Keywords: zirconium butoxide, zirconium alkoxide solutions, EXAFS
Pages: 80-87

Abstract >>
The structure of particles in zirconium n-butoxide solutions in n-butyl alcohol is determined by means of EXAFS, SAXS, and molecular mechanics modeling. Zirconium atoms are found to be bonded to each other via the oxygen atom and to form large anisotropic particles in the solution. Primary particles have a shape close to spherical; their diameter together with the solvate shell is 28.9 Å. These particles then aggregate into anisotropic structures. During solution aging under normal conditions without contact with the atmosphere, the particle anisotropy increases because of the aggregation of complexes. When the solution concentration decreases, the particles are divided into primary spherical particles with a characteristic size of 28.9 Å. The described changes are confirmed by a decrease in the number of Zr-Zr distances of 4.8 Å and 5.1 Å, which according to the EXAFS data, correspond to the bonds between the primary particles. The characteristic maximum sizes of particles in solutions with concentrations from 0.1 g to 0.003 g ZrO2/ml are 160-80 Å.



11.
STRUCTURE OF IRON(III)-CONTAINING COMPLEXES BASED ON THE AZOMETHINE - 4,4′-DODECYLOXY-BENZOYLOXYBENZOYL-4-SALICYLIDENE-N′-ETHYL-N-ETHYLENEDIAMINE MOLECULE

M. S. Gruzdev1, U. V. Chervonova2, A. M. Kolker3, N. E. Domracheva4
1
2
3
4
Keywords: Schiff base, structure, mass-spectrometry, IR spectroscopy
Pages: 88-95

Abstract >>
Iron(III)-containing complexes with an asymmetric tridentate azomethine 4,4′-dodecyloxybenzoyloxybenzoyl-4-salicylidene-N′-ethyl-N-ethylenediamine ligand with Cl-, and BF counterions are synthesized. The presence of the complexation ion is confirmed by the far FTIR spectra. The structure of the compounds is determined by the matrix-assisted laser desorption/ionization-time of flight (MALDI-ToF) method. The results of mass-spectrmetric studies are consistent with the elemental analysis data. The complexation of iron salts with the asymmetric tridentate ligand is found to yield compounds of the 1:1 composition with octahedral packing of iron in the complex.



12.
DIELECTRIC PROPERTIES OF A DIPOLAR HARD SPHERE LIQUID: ASSOCIATION EQUILIBRIA THEORY

G. B. Litinskii
Keywords: association equilibria theory, association constant, Kirkwood factor, dipolar hard sphere fluid
Pages: 96-100

Abstract >>
The hindered rotation model is used to generalize the association equilibria theory for the case of a dense dipolar hard sphere (DHS) liquid. The derived expressions for the orientation constant of association and the Kirkwood factor of a DHS liquid are well consistent with machine experiments in the high temperature region.



13.
VOLUME PROPERTIES OF A TERNARY SYSTEM: WATER-UREA-AMINO ACID. DILUTE AND CONCENTRATED SOLUTIONS

V. P. Korolev
Keywords: urea, amino acid, aqueous solutions, partial volumes
Pages: 101-109

Abstract >>
Partial molar volumes  of amino acids in an aqueous urea solution are studied. For a saturated urea solution  equals the molar volume of the amino acid, therefore, in the saturated solution, the amino acid dissolves without changing the system volume. Hydrophobic effects are manifested in the volumetric characteristics only in dilute (<1 mol/kg) urea solutions. Within a three-layer hydration model, the numbers of amino acid hydration are found. By the example of alanine and leucine, it is shown that their decrease with increasing urea concentration is determined by a zwitterionic moiety and does not depend on the size of the hydrocarbon radical of the amino acid.



14.
A second attempt to establish an analytical expression to steam-water dipole orientation parameter using the Boubaker Polynomials Expansion Scheme

W.X. Yue1, H. Ko??ak2, D.H. Zhang3, A. Y??ld??r??m4
1 Department of Mathematics Lanzhou City University
2 Ege University Bornova
3 South China University, zhangdahong2003@yahoo.cn
4 Ege University Bornova
Keywords: steam-water, BPES; permanent dipole moment, analytical expression
Pages: 110-114

Abstract >>
In this paper, an analytical expression to the steam-water dipole orientation parameter is proposed. The calculations have been carried out under the presumptions that: the electric properties of the water molecules are characterized completely by a permanent dipole moment and
a constant scalar polarizability, that translational fluctuations may be neglected, and that the positions are orientation-free. The results have been presented in the form of continuous and integrable expressions which could be easily compared to precedent studies as well as involved in similar analytical models



15.
CRYSTAL STRUCTURE OF NICKEL PARATUNGSTATE B Ni5[W12O40()2]37H2O

S. V. Radio1, G. M. Rozantsev2, V. N. Baumer3, O. V. Shishkin4
1
2
3
4
Keywords: isopolytungstate, paratungstate B, crystal structure, FTIR spectroscopy, single crystal X-ray analysis
Pages: 115-121

Abstract >>
From the solution of the system Na2WO4-HNO3-Ni(NO3)2-H2O acidified to Z = ν(H+)/ν(WO) = 1.29, the green crystals of nickel paratungstate B Ni5[W12O40()2]37H2O are isolated. By FTIR spectroscopy the isopoly anion is shown to belong to the structural type of paratungstate B. Using single crystal X-ray analysis, the structure of Ni5[W12O40()2]37H2O is solved (Mr = 3840.36, monoclinic, P21/c space group, a = 21.9061(6) Å, b = 14.9297(4) Å, c = 22.1391(6) Å, β = 107.609(3), V = 6901.4(3) Å3 at T = 293 K, Z = 4, dx = 3.696 g/cm3, F000 = 6944, μ = 21.368 mm-1, -33 ≤ h ≤ 33, -22 ≤ k ≤ 22, -33 ≤ l ≤33; the final uncertainty values for the observed reflections are RF = 0.0532, wR2 = 0.0831 (RF = 0.1088, wR2 = 0.0894 over all independent reflections), S = 0.978; CSD-421468).



16.
STRUCTURE OF ALUMINUM(III) DIPIVALOYLMETHANATE AlO6C33H57

P. A. Stabnikov1, A. I. Smolentsev2, N. V. Pervukhina3, O. S. Koshcheeva4, L. N. Komissarova5, S. V. Borisov6
1
2
3
4
5
6
Keywords: aluminum dipivaloylmethanate, crystal structure, packings of metal tris- dipivaloylmethanates
Pages: 122-128

Abstract >>
The structure of aluminum(III) tris-dipivaloylmethanate (Bruker Nonius X8 Apex diffractometer with a 4K CCD detector, λMoKα, graphite monochromator, T = 150(2) K) is determined, and the synthetic procedure for its preparation is suggested. Crystal data are: C2/c space group, a = 28.1587(12) Å, b = 18.5170(7) Å, c = 21.5332(8) Å, β = 97.573(1), V = 11129.8(8) Å3, Z = 12, dx = 1.033 g/cm3, R = 6.93. The complex has a molecular structure; the aluminum atom is octahedrally surrounded by six oxygen atoms of three chelating ligands; Al-O distances are 1.860(2)-1.873(2) Å; O-Al-O angles fall within 88.08(9)-91.96(10) and 177.93(9)-179.83(14). The known crystal packings of metal tris-dipivaloylmethanates are analyzed. Three types of the arrangement of the molecules in the crystals denoted as α, β, and γ are identified.



17.
STRUCTURE AND THERMAL PROPERTIES OF [Ir(NH3)5Cl]x[Rh(NH3)5Cl]1-xMO4 (x = 0.5, 1; M = Mo, W)

E. A. Shusharina1, P. E. Plyusnin2, S. P. Khranenko3, S. A. Gromilov4
1
2
3
4
Keywords: tungsten, molybdenum, iridium, rhodium, complex salt, crystal chemistry, single-crystal X-ray crystallography, thermal analysis
Pages: 129-136

Abstract >>
Complex salts [Ir(NH3)5Cl]x[Rh(NH3)5Cl]1-xMO4 (x = 0.5, 1; M = Mo, W) are synthesized and their thermal properties are studied. The crystal structures are determined for [Ir(NH3)5Cl]WO4 and [Ir(NH3)5Cl]MoO4. In the structures, the ions are linked by N-HO hydrogen bonds, the shortest ones being 2.868(2)-3.422(2) Å and 2.860(4)-3.434(3) Å respectively. The thermal properties of the complex salts are studied in the hydrogen atmosphere and in hydrogen-helium mixtures. It is demonstrated that the final products are the mixtures of nanocrystalline powders of Ir and binary or ternary solid solutions with the hcp lattice.



18.
CRYSTAL STRUCTURES OF trans-DICHLOROBIS(ETHYLEN- DIAMINE) RHODIUM(III) WITH UNIVALENT ANIONS

I. A. Baidina1, S. N. Vorob'eva2, A. I. Smolentsev3, A. V. Belyaev4
1
2
3
4
Keywords: rhodium, trans-tetramines, coordination compounds, crystal structure
Pages: 137-143

Abstract >>
The crystal structures of the compounds trans-[Rh(en)2Cl2]Cl2.H5O2 (I), trans-[Rh(en)2Cl2]ClO4 (II), and trans-[Rh(en)2Cl2]ReO4 (III) are determined. The crystal data are: I, a = 10.860(3) Å, b = 7.795(2) Å, c = 9.023(3) Å; β = 111.56(10), P21/ space group, Z = 4, dx = 1.875 g/cm3; II, a = 6.593(2) Å, b = 8.309(3) Å, c = 11.922(4) Å, α = 83.55(10), β = 79.80(10), γ = 75.38(10), space group, Z = 2, dx = 2.106 g/cm3; III, a = 6.533(2) Å, b = 16.391(4) Å, c = 12.411(3) Å; β = 98.30(10), P21/c space group, Z = 4, dx = 2.749 g/cm3. The compounds are examined by IR spectroscopy and powder XRD. The solubility of the isolated crystalline phases in water decreases in the following order: trans-[Rh(en)2Cl2]Cl2H5O2 > trans-[Rh(en)2Cl2]ClO4 > trans-[Rh(en)2Cl2]ReO4.



19.
STRUCTURE AND THERMAL PROPERTIES OF DOUBLE COMPLEX SALTS [RuNO(NH3)4(H2O)]2[MCl4]Cl42H2O, = Pt, Pd

O. A. Plyusnina1, V. A. Emel'yanov2, I. A. Baidina3, P. E. Plyusnin4, S. A. Gromilov5
1
2
3
4
5
Keywords: double complex salt, ruthenium, platinum, palladium, X-ray crystallography, crystal chemistry, thermal decomposition
Pages: 144-154

Abstract >>
Double complex salts (DCS) [RuNO(NH3)4(H2O)]2[MCl4]Cl42H2O, M = Pt (I) and Pd (II), are prepared and characterized using IR spectroscopy, single crystal and powder X-ray diffraction, and thermogravimetric analysis. Crystalline phases of I and II are isostructural (P2(1)/n space group) and have the following crystallographic characteristics: a = 6.689 Å, b = 15.609 Å, c = 12.348 Å, V = 1289.1 Å3, Z = 2, dx = 2.425 g/cm3 (I) and a = 6.637 Å, b = 15.521 Å, c = 12.244 Å, V = 1261.2 Å3, Z = 2, dx = 2.255 g/cm3 (II). The thermolysis of the obtained DCS in the hydrogen atmosphere affords two-phase mixtures of limited solid solutions of the metals: hcp for ruthenium-based ones and fcc for Pt or Pd based solutions. On decomposition in the helium atmosphere the products contain a minor amount of RuO2. For the phases obtained during thermolysis the parameters are determined and the compositions are estimated. The heating of I to 400C in the helium-air atmosphere yields a nanocrystalline composite Pt+RuO2 with CSR of ~20 nm.



20.
Ru2(CO)4{OOC(CH2)nCH3}2L2 sawhorse-type complexes containing μ22-carboxylato ligands derived from saturated fatty acids

J.P. Johnpeter1, B. Therrien2
1 Institut de Chimie Université de Neuchâtel
2 Institut de Chimie Université de Neuchâtel, bruno.therrien@unine.ch
Keywords: carbonyl ligands, carboxylato bridges, fatty acids, dinuclear complexes, ruthenium
Pages: 155-163

Abstract >>
The thermal reaction of Ru3(CO)12 with the saturated fatty acids (heptanoic, nonanoic, decanoic, tridecanoic, tetradecanoic, heptadecanoic, octadecanoic) in refluxing tetrahydrofuran, followed by addition of triphenylphosphine (PPh3) or pyridine (C5H5N), gives the dinuclear complexes Ru2(CO)4{OOC(CH2)nCH3}2L2 (1: n = 5, 2: n = 7, 3: n = 8, 4: n = 11, 5: n = 12,
6: n = 15, 7: n = 16; a: L = NC5H5, b: L = PPh3). The single-crystal structure analysis of 1b, 2a, 3a, 4a and 5a reveals a dinuclear Ru2(CO)4 sawhorse structure, the diruthenium backbone being bridged by the carboxylato ligands, while the two L ligands occupy the axial positions at the ruthenium atoms. In 2a, π-π stacking interactions between adjacent pyridyl units of symmetry related molecules prevail, while in the longer alkyl chain derivatives 3a, 4a and 5a, additional van der Waals and electrostatic interactions between the alkyl chains take place as well in the packing arrangement of the molecules, thus giving rise to layers of parallel alkyl chains in the crystal.



21.
CRYSTAL STRUCTURE OF A SILVER(I) COMPLEX {[Ag(N-METHYLTHIOUREA)2]NO3}n EXHIBITING INFINITE CHAINS OF AgS4 TETRAHEDRA

Habib-ur-rehman1, S. Ahmad2, H. Ajaz3, M. Hanif4, M. Altaf5, H. Stoeckli-evans6
1 Exxelis Limited ETTC/Biospace
2 Department of Chemistry University of Engineering and Technology, saeed_a786@hotmail.com
3 Department of Chemistry University of Engineering and Technology
4 Department of Chemistry University of Engineering and Technology
5 Institute of Physics University of Neuchâtel
6 Institute of Physics University of Neuchâtel
Keywords: Silver(I) complexes, N-methylthiourea, crystal structure
Pages: 164-169

Abstract >>
A polymeric silver(I) complex, bis(N-methylthiourea)silver(I) nitrate, {[Ag(Metu)2]NO3}n is prepared and its crystal structure is determined by X-ray crystallography. The compound crystallizes in the monoclinic C2/c space group. In the structure, distorted AgS4 tetrahedra are linked through the sulfur atoms of the Metu ligand to form isolated infinite chains of the type [Ag(SR)2]. The cationic chains are separated from each other by nitrate ions that do not coordinate to the metal ion. The chains are bridged via N-HO hydrogen bonds involving the nitrate ions. The complex exhibits an Ag---Ag separation of ~3.21 Å indicating the existence of significant argentophilic interactions. An upfield shift in the >C=S resonance of Metu in 13C NMR and downfield shift in the N-H resonance in 1H NMR are consistent with sulfur coordination to silver(I).



22.
CRYSTAL STRUCTURES OF (H7O3)2[(Mo6Cl7.22I0.78)Cl6]3H2O, (H9O4)2[(Mo6Cl6.66I1.34)Cl6] AND (H5O2)2[(Mo6Cl6.36I1.64)Cl6]2H2O: DRASTIC CHANGES IN PACKING CAUSED BY SMAL VARIATIONS IN THE CHEMICAL COMPOSITIONS OF THE CLUSTER CORES

M. N. Sokolov1, . . Mikhailov2, . V. Virovets3, V. P. Fedin4
1
2
3
4
Keywords: molybdenum, iodine, chlorine, clusters, X-ray structure, packing topology, mass-spectra
Pages: 170-175

Abstract >>
The crystal structures of three new chloride-iodide cluster complexes of Mo(II) of the compositions (H7O3)2[(Mo6Cl7.22I0.78)Cl6]3H2O (1), (H9O4)2[(Mo6Cl6.66I1.34)Cl6] (2), and (H5O2)2[(Mo6Cl6.36I1.64)Cl6]2H2O (3) are determined. All cluster anions in 1-3 are derived from octahedral halide-bridged clusters {Mo63-Hal)8}4+ (Hal = Cl, I). The iodide ligands are disordered over three μ3-positions. According to mass-spectrometry, all these compounds are solid solutions of the hydroxonium salts of [(Mo6Cl6I2)Cl6]2- and [(Mo6Cl7I)Cl6]2-. Small changes in the iodine content of the cluster cores give rise to changes in the composition of the hydroxonium cations, in the hydrogen bonding network and can lead to changes in the structural type. The cluster anions are packed according to the fcc (1, 3) or hcp (2) motifs.



23.
coordination polymers based on [Re6Se8(CN)6]4- clUsTer anion, LANTHANIDE CATIONS, AND tetraatomic alcohol ERYTHRITOL

M. S. Tarasenko1, A. Y. Ledneva2, D. Y. Naumov3, N. G. Naumov4, V. E. Fedorov5
1
2
3
4
5
Keywords: rhenium, octahedral cluster, cyanide complex, lanthanides, synthesis, crystal structure, polyatomic alcohol
Pages: 176-183

Abstract >>
By the interaction of aqueous solutions of salts of the [Re6Se8(CN)6]4- cluster anion with salts of Nd(III), Tb(III), and Yb(III) lanthanides in the presence of tetraatomic alcohol erythritol (butane-1,2R,3S,4-tetraol) three new compounds are obtained: K[Nd(C4H10O4)(H2O)4{Re6Se8(CN)6}]4H2O (space group, a = 11.544 Å, b = 13.643 Å, c = 13.838 Å, α = 111.97, β = 108.08, γ = 90.08) (1); [{Yb2(C4H9O4)2×(H2O)2}{Re6Se8(CN)6}]5H2O ( space group, a = 10.308 Å, b = 10.505 Å, c = 11.154 Å, α = 88.21, β = 81.83, γ = 78.50) (2); [{Tb2(C4H9O4)2(C4H10O4)}{Re6Se8(CN)6}]4H2O (space group, a = 10.002 Å, b = 10.276 Å, c = 11.762 Å, α = 91.32, β = 104.01, γ = 106.02) (3). The structures of these compounds are the coordination polymers (chain (2) and grids (1 and 3)) with different coordination modes of erythritol to the lanthanide cations.



24.
STRUCTURE OF THE PRODUCT OF INTERACTION OF N-VINYLCAPROLACTAM WITH 3-CHLOROPHENYLISOCYANATE

A. R. Zaripova1, R. R. Spiridonova2, O. I. Gnezdilov3, I. K. Rizvanov4, I. A. Litvinov5, A. T. Gubaydulin6, Y. D. Samuilov7
1
2
3
4
5
6
7
Keywords: N-vinylcaprolactam, 3-chlorophenylisocyanate, chromato-mass spectrometry analysis, single crystal X-ray diffraction
Pages: 184-189

Abstract >>
The [2+2]-cycloaddition reaction of N-vinylcaprolactam with 3-chlorophenylcyanate yielding 1-(3-chlorophenyl)-4-[1-perhydroazepinone-2]-azetidinone-2 is studied. The structure of the obtained compound is determined by single crystal XRD.



25.
GOSSYPOL CLATHRATES: STRUCTURE AND THERMAL BEHAVIOR OF GOSSYPOL SOLVATES WITH TWO PICOLINE ISOMERS

S. A. Talipov1, M. T. Khonkeldieva2, L. Y. Izotova3, Z. G. Tilyakov4, B. T. Ibragimov5
1
2
3
4
5
Keywords: gossypol, 4-picoline, 2-picoline, clathrate formation, crystal structure
Pages: 190-196

Abstract >>
Gossypol forms stable solvates with 4- and 2-picolines at room temperature. The solvates are investigated by single crystal X-ray diffraction and thermal analysis. Solvate crystals of gossypol with 4-picoline (1) have the 1:3 composition (gossypol:4-picoline) and crystallize in the P21/ space group. This substance is isostructural to a trisolvate of gossypol with pyridine. Solvate crystals of gossypol with 2-picoline (2) have the 1:4 composition (gossypol:2-picoline) and crystallize in the P-1 space group. The unit cell parameters for the investigated structures are as follows: 1 monoclinic crystals, C30H30O83C6H7N, a = 10.7530(1) Å, b = 20.7834(3) Å, c = 19.1166(2) Å, β = 95.537(1), V = 4252.32(9) Å3, M = 797.92, Z = 4, dx = 1.246 g/cm3, and R = 0.0489 for 4102 reflections; 2 triclinic crystals, C30H30O84C6H7N, a = 11.467(1) Å, b = 14.962(2) Å, c = 15.570(3) Å, α = 75.62(1), β = 69.83(1), γ = 79.58(1), V = 2414.6(7) Å3, M = 891.04, Z = 2, dx = 1.226 g/cm3, and R = 0.0528 for 3779 reflections. The results of the single crystal XRD and thermal analysis confirm that gossypol with 4-picoline forms a trisolvat, and a tetrasolvate with 2-picoline. The transition from 4-picoline to 2-picoline proves to change the type of the host-guest association from one-dimensional to zero-dimensional, i.e., to lead to a new crystal structure. Desolvation of compound 2 begins at a lower temperature than that for compound 1, which is explained by their different crystal structures.



26.
GOSSYPOL CLATHRATES: STRUCTURE AND THERMAL BEHAVIOR OF THE GOSSYPOL ACRIDINE COMPLEX

M. T. Khonkeldieva1, S. A. Talipov2, L. Y. Izotova3, Z. G. Tilyakov4, B. T. Ibragimov5, É. N. Kurtaliev6
1
2
3
4
5
6
Keywords: gossypol, acridine, clathrate formation, crystal structure
Pages: 197-200

Abstract >>
The natural compound gossypol forms a stable clathrate with acridine. The composition of the clathrate is C30H30O80.5C13H9N. The unit cell is monoclinic, C2/c space group, a = 11.3213(3) Å, b = 30.5957(13) Å, c = 17.0824(4) Å, γ = 94.153(2), V = 5901.5(3) Å3, M = 1153.24, Z = 8, dx = 1.369 g/cm3, and R = 0.0413 for 4726 reflections. The structure of the clathrate allows one to refer this compound to the ethyl acetate isomorphic host-guest group of gossypol complexes.



27.
X-RAY DIFFRACTION STUDY OF CRYSTAL AND MOLECULAR STRUCTURE OF ACETYLACETONE AZOCOMPOUND - [C11H11N2O2F1]

M. A. Magerramov1, R. A. Alieva2, R. Z. Nazarova3, F. M. Chyragov4, K. A. Potekhin5
1
2
3
4
5
Keywords: single crystal X-ray diffraction analysis, acetylacetone azoderivatives, intermolecular hydrogen bonds, packing of the 3-[4-fluorophenylazopentadione]-2,4
Pages: 201-205

Abstract >>
The 3-[4-fluorophenylazopentandion]-2,4 reagent is synthesized based on acetylacetone, and its crystal and molecular structure is studied by X-ray diffraction. It is found that [C11H11N2O2F] crystals 1 belong to the monoclinic symmetry, C2/c space group. The unit cell parameters of 1 are a = 18.827(3) Å, b = 12.839(2) Å, c = 26.475(5) Å, β = 104.834(2). The analysis shows that the reagent is present in the solution as well as in the crystal. A comparative analysis of these three structures with the reported data is carried out.



28.
Crystal structure of [Cu(en)2](ReO4)2

E. A. Shusharina1, S. P. Khranenko2, S. A. Gromilov3
1
2
3
Keywords: copper, rhenium, ethylenediamine, rhenium, thermal decomposition, crystal chemistry, single crystal X-ray diffraction analysis
Pages: 206-208

Abstract >>
At T = 150 K the crystal structure of [u(en)2](ReO4)2 (en is ethylenediamine) is studied: a = 6.6229(1) Å, b = 14.2968(3) Å, c = 7.4859(2) Å, β = 102.415(1), V = 692.24(3) Å3, P21/c space group, Z = 2, dx = 3.282 g/cm3. Packing of complex cations is shown to be single layered and pseudohexagonal. Perrhenate anions are located between these layers and additionally coordinate copper atoms with CuO distances being 2.504(3) Å.



29.
CRYSTAL STRUCTURE OF n-phenyl-n′-isopropyl-P-Phenylenediamine

É. A. Mukhutdinov1, A. T. Gubaidullin2, D. B. Krivolapov3, I. A. Litvinov4, A. A. Mukhutdinov5
1
2
3
4
5
Keywords: N-phenyl-N?-isopropyl-p-phenylenediamine, single crystal X-ray diffraction
Pages: 209-210

Abstract >>
We have previously reported the results of studies of the hydrogen bond nature in N-phenyl-N′-isopropyl-p-phenylenediamine by a quantum chemistry method and FTIR spectroscopy [1-3]. It is shown that the IR spectrum of N-phenyl-N′-isopropyl-p-phenylenediamine has IR bands in the νNH absorption region at 3380 cm-1 and 3400 cm-1 corresponding to the NH groups involved in hydrogen bonding.



30.
Crystal Structure of Indium(III) Schiff Base Complex

G.Y.S.K. Swamy1, K. Ravikumar2
1 Laboratory of X-ray Crystallography Indian Institute of Chemical Technology, swamygundimella@yahoo.com
2 Laboratory of X-ray Crystallography Indian Institute of Chemical Technology
Keywords: crystal structure, Schiff base, metal complex, X-ray diffraction, hydrogen bonding
Pages: 211-214

Abstract >>
The title compound [In(C22H30N4O4)]Cl (I) bis[(N-salicylidene-N′-(2-hydroxyethyl)ethyleneediamine)indium(III) chloride is prepared, and its crystal structure is determined by single crystal X-ray diffraction at room temperature. The complex crystallizes in the monoclinic space group P21/n, a = 9.9704(6), b = 24.9554(15), c = 10.5707(6) Å, β = 116.46(2), V =
= 2354.6(2), Z = 4. The X-ray analysis reveals that the InIII ion is surrounded by four nitrogen and two oxygen atoms from two ligands leading to a distorted octahedral geometry. The molecule has the form of tongs at a junction point with the metal. Five membered rings adopt envelope conformation. In the crystal structure, the molecules are linked via N-HCl, O-HO, O-HCl, and C-HCl intermolecular interactions. The structure is further stabilized by C-Hπ (arene) interactions.



31.
Crystal Structure of Diammine(malonato)palladium(II)

Q.-S. Ye1, M.-J. Xie2, W.-P. Liu3, W.-ZH. Xia4, X.-ZH. Chen5, Q.-W. Chang6, Y. Yu7
1 State Key Lab of Advanced Technologies for PGMs Kunming Institute of Precious Metals, liuweiping0917@126.com
2 Department of Chemistry Yunnan University
3 State Key Lab of Advanced Technologies for PGMs Kunming Institute of Precious Metals
4 State Key Lab of Advanced Technologies for PGMs Kunming Institute of Precious Metals
5 State Key Lab of Advanced Technologies for PGMs Kunming Institute of Precious Metals
6 State Key Lab of Advanced Technologies for PGMs Kunming Institute of Precious Metals
7 State Key Lab of Advanced Technologies for PGMs Kunming Institute of Precious Metals
Keywords: palladium, malonate, ammonia, crystal structure, synthesis
Pages: 215-217

Abstract >>
Diammine(malonato)palladium(II) is synthesized by the reaction of [Pd(NH3)4](NO3)2 with malonic acid, and its crystal structure is determined by single crystal X-ray diffraction. Distorted coordination square of the Pd(II) atom is formed by two N atoms of two ammonia molecules and two O atoms of bidentate malonate ligand. The average Pd-N and Pd-O distances are 2.018(7) Å and 2.014(2) Å, respectively. The molecules are stacked in such a way that the planes of coordination squares are parallel with the Pd?KPd distances between the nearest neighbors in a stack of 4.039 Å.



32.
A TEMPERATURE STUDY OF ENAMINOIMINE TAUTOMERISM IN THE COCRYSTALS OF 3-(1-AMINO-2,2,2-TRIFLUOROETHYLIDENE)- 2-IMINO-1,1,4,5,6,7-HEXAFLUOROINDANE WITH DIOXANE BY SINGLE CRYSTAL XRD

T. V. Rybalova1, V. M. Karpov2, Y. V. Gatilov3
1
2
3
Keywords: temperature single crystal X-ray diffraction, polyfluorinated enaminoimines, indane, indene, tautomers, equilibrium
Pages: 218-222

Abstract >>
Single crystal X-ray diffraction is used to investigate the cocrystals of 3-(1-amino-2,2,2-trifluoroethylidene)-2-imino-1,1,4,5,6,7-hexafluoroindane (1) with 1,4-dioxane at temperatures of 100 K, 200 K, and 273 K. The study shows that compound 1 is in equilibrium with its tautomer: 2-amino-3-(1-imino-2,2,2-trifluoroethyl)-1,1,4,5,6,7-hexafluoroindene (1a).



33.
CRYSTAL STRUCTURE AND LUMINISCENT PROPERTIES OF 2,2-DIFLUORO-4-(9-FLUORENE-2-YL)-6-METHYL-1,3,2-DIOXABORINE

B. V. Bukvetskii1, E. V. Fedorenko2, A. G. Mirochnik3
1
2
3
Keywords: ? diketonates of boron difluoride, 2,2-difluoro-4-(9-fluorene-2-yl)-6-methyl-1,3,2-dioxaborine, crystal structure, luminescence
Pages: 223-227

Abstract >>
The crystal structure of 2,2-difluoro-4-(9-fluorene-2-yl)-6-methyl-1,3,2-dioxaborine (13H9COCH×COCH3BF2) (1) is determined. The structural and spectral luminescent characteristics of 1 are compared to those of its electron analogue: 2,2-difluoro-4-(4-phenylphenyl)-6-methyl-1,3,2-dioxaborine (6H5C6H4×COCHCOCH3BF2).