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Journal of Structural Chemistry

2014 year, number 1

1.
STRUCTURE OF WATER (H2O)6 AND AMMONIUM (NH3)13 CLUSTERS WITH AN EXCESS ELECTRON: QUANTUM CHEMICAL STUDIES

I. I. Zakharov1,2
1V. Dal East Ukrainian National University, Severodonetsk, Ukraine
2Technological Institute
Keywords: quantum chemical DFT and 2 calculations, molecular clusters of water and ammonium, solvated electron model

Abstract >>
The B3LYP method within DFT and the ab initio 2 method with an extended 6-311++G(3df,3pd) basis set are employed to calculate the adiabatic bound state of an excess electron in (H2O)6¯water and (NH3)13¯ ammonium clusters. Adiabatic electron affinity of (H2)6 and (NH3)13 clusters is 0.03—0.18 eV and 0.18 eV respectively. The calculated vertical binding energies of the excess electron in anionic clusters ((H2O)6¯ 0.37÷0.66 eV and (NH3)13¯ 0.26 eV) agree well with the experimental values of 0.50 eV and 0.22 eV obtained from photoelectron spectra. A cavity model of solvated electrons in water and ammonium is considered.
																								



2.
EFFECT OF 5-METHYLRESORCINOL ON SPIN CONVERSION IN MOLECULAR OXYGEN

G. I. Kobzev, A. N. Kazaeva, S. Futterknecht
Orenburg State University, Orenburg
Keywords: 5-methylresorcinol, excited oxygen states, potential energy surface (PES), spin conversion

Abstract >>
Geometric parameters of 5-methylresorcinol (MR) molecules in different spin states (1,3,5MR) and its complexes with oxygen (1,3(O2–MR)) are determined within the DFT/B3LYP method. Cross-sections of potential energy surfaces of the formation reaction of the intermolecular complex 1,3(O2MR) are plotted in MCSCF functions by the MRCI method. With regard to the spin-orbit interaction the moments of spin-allowed and spin-forbidden transitions of the complexes are calculated and the possibility of spin conversion in 3O2 under the effect of MR is analyzed.
																								



3.
STRUCTURE AND STABILITY OF MOLECULAR AND IONIC COMPLEXES OF AlCl3 WITH PYRAZINE AND 4,4'-BIPYRIDYL

E. I. Davydova1, A. Yu. Timoshkin1, G. Frenking2
1St. Petersburg State University, St. Petersburg, Russia
2Philipps-Universität Marburg, Marburg, Germany
Keywords: quantum chemical calculations, molecular complexes, ionic complexes, aluminum chloride, pyrazine, 4,4'-bipyridyl, structure, stability

Abstract >>
Structural and thermodynamic characteristics of molecular and ionic complexes of aluminum trichloride with pyrazine (pyz) and 4,4'-bipyridyl (bipy) are calculated at the RI-BP86/def2-SVP level. It is found that for molecular 2AlCl3·3L and 4AlCl33L complexes an energy difference between isomers does not exceed 4 kJ/mol, and the rotation barrier of the AlCl3 moiety relative to the N–AlN bond does not exceed 24 kJ/mol. A comparison of the stability of molecular and ionic complexes of aluminum in the gas phase shows that the maximum energy difference is ~60 kJ/mol. For L = pyz the molecular complex is more stable whereas for L = bipy it is the ionic one.
																								



4.
A QUANTUM CHEMICAL STUDY OF THE STRUCTURE OF DODECASILSEQUIOXANE H12Si12O18

S. G. Semenov, M. E. Bedrina
St. Petersburg State University, St. Petersburg, Russia
Keywords: dodecasilsequioxane, endocomplexes, symmetry, structure, ionization, B3LYP, PBE0, MP2(full), cc-pVTZ

Abstract >>
Quantum chemical B3LYP/cc-pVTZ, PBE0/cc-pVTZ, and MP2(full)/6-311G(d,p) methods are used to calculate the structural parameters of dodecasilsequioxane H12Si12O18 and the H12Si12O18+ cation. According to DFT/cc-pVTZ calculations the energy of H12Si12O18(D6h) is 1.3-1.7 kcal/mol higher than the energy of H12Si12O18(D2d). A reduction of the basis set results in a greater energy difference of H12Si12O18 isomers. For the cation 2B2u and 2B1 electronic states are obtained, which correspond to symmetric equilibrium structures H12Si12O18+ (D6h) and (D2) respectively. For the He@H12Si12O18 endocomplex the D2d symmetry is obtained; for He2@H12Si12O18 the D2h symmetry; and for H2@H12Si12O18 the D6h symmetry.
																								



5.
DFT STUDIES ON THE TETRANUCLEAR CUBANE COMPLEX [Ni4(ampd)4(Cl4)]·MeCN

G. Abbas1, Mariya Al Rashida2, A. Irfan3, U. Ali Rana4, I. Shakir4
1Interdisciplinary Research Centre in Biomedical Materials COMSATS Institute of Information Technology, Lahore, Pakistan
2Forman Christian College University, Lahore, Pakistan
3King Khalid University, Abha, Saudi Arabia
4College of Engendering, King Sand university, Riyadh, Saudi Arabia
Keywords: Ni(II) cubane, 2-amino-2-methyl-2,3-propandiol, single crystal X-ray crystallography, density functional theory, time-dependent density functional theory

Abstract >>
Density functional theory (DFT) is used to investigate the structural properties of Ni(II) cubane [Ni4(ampdH)4Cl4]·MeCN. The structural features and ground state geometry calculations are computed at the B3LYP/6-31G* (LANL2DZ) level of theory. We shed light on the highest occupied molecular orbital and lowest unoccupied molecular orbital. The absorption spectrum is calculated using time-dependent DFT. The absorption wavelengths are calculated using different functionals, i.e., pw91pw91, B3LYP, BHandHLYP, CAM-B3LYP, LC-BLYP, and M06. The LC-BLYP is in good agreement with the experimental data.
																								



6.
APPLICATION OF THE AMYR CALCULATING METHOD ON QUINOXALINE, 3-CHLOROQUINOXALINE, AND 3-METHYLQUINOXALINE IN THE INTERACTION WITH n WATER MOLECULES ( n VARIES FROM 1 TO 6)

A. El Assyry, B. Benali, A. Boucetta, B. Lakhrissi
Université Ibn Tofail, Kénitra, Morocco
Keywords: quinoxaline, 3-chloroquinoxaline, 3-methylquinoxaline, AMYR, interaction energies, conformations

Abstract >>
AMYR is a computer program for the calculation of molecular associations using Fraga's pairwise atom-atom potential. The interaction energy is evaluated through a 1/R expansion. A pairwise dispersion energy term is included in the potential and corrected by a damping function. The program carries out energy minimizations through variable metric methods. The new version allows for the stationary point analysis of the intermolecular potential by means of the Hessian eigenvalues. AMYR model is used for the first time in a calculation of quinoxaline, 3-chloroquinoxaline, and 3-methylquinoxaline molecules interacting with some water molecules. Intermolecular interaction energies are obtained and the stable conformation is determined in each case. The change conformation was considered at α ≈ (CNC) angle when the solute molecules are surrounded by n water molecules (1 ≤ n ≤ 6).
																								



7.
SPIN-CROSSOVER IN COMPLEXES OF IRON(II) CARBORANES WITH TRIS(PYRAZOL-1-YL)METHANE

O. G. Shakirova1, V. A. Daletskii2, L. G. Lavrenova2,3, V. A. Varnek2, D. A. Rudakov4, V. I. Potkin4
1Komsomolsk-on-Amur State Technical University, Komsomolsk-on-Amur
2A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
3Novosibirsk State University, Novosibirsk
4Institute of Physico-Organic Chemistry, National Academy of Sciences of Belarus, Minsk
Keywords: synthesis, iron(II) complexes, carboranes, tris(pyrazol-1-yl)methane, spin-crossover, magnetochemistry, electron, IR, and Mössbauer spectroscopy

Abstract >>
Synthesis procedures for coordination compounds of iron(II) 1,5,6,10-tetra(R)-7,8-dicarba- nido-undecaborates(-1) (carboranes) with tris(pyrazol-1-yl)methane (HC(pz)3) of the composition [Fe{HC(pz)3}2]A2· nH2O ( = (7,8-2B9H12) ( I), (1,5,6,10-Br4-7,8-2B9H8) ( II), (1,5,6,10-I4-7,8-2B9H8) ( III), n = 0-2) are developed. The compounds are studied by static magnetic susceptibility in the temperature range of 160-500 K, electron (diffuse reflectance spectra), IR, and Mössbauer spectroscopy methods. It is shown that the complexes have high-temperature spin-crossover 1152. Transition temperatures ( ) for I-III are 370 K, 380 K, and 400 K respectively. Spin-crossover is accompanied by thermochromism (color change: pink ⇔ white).
																								



8.
CRYSTALLOGRAPHIC AND THEORETICAL STUDIES OF 1-(1-NAPTHYL)-2-THIOUREA WITH INTERMOLECULAR N-H...S HETEROATOM INTERACTION AND N-H...π INTERACTION

M.A. AlDamen1, M. Sinnokrot2
1The University of Jordan, Amman, Jordan
2The Petroleum Institute, Abu Dhabi 2533 UAE
Keywords: 1-(1-naphthyl)-2-thiourea, SH-N hydrogen bond, interaction energy, ab initio, RIMP2, B3LYP

Abstract >>
A single crystal X-ray diffraction study of 1-(1-naphthyl)-2-thiourea (1) C11H10N2S indicates crystallization in the monoclinic space group C2/c, Z = 8, with unit cell parameters a = 15.3864(14) Å, b = 7.6090(7) Å, c = 17.0836(16) Å, β = 91.7420(30)°. In the crystal structure, two components of 1 are connected via intermolecular NH…S hydrogen bonds (the NS distance of 3.371 Å). In 1 there is an NHπ interaction (with the Nπ distance of 3.804 Å and a possible N-Hπ distance of 3.196 Å). The calculations of 1 at the B3LYP/ cc-pVTZ, RHF/ cc-pVTZ, RIMP2/ cc-pVDZ, and RIMP2/ cc-pVTZ levels of theory can almost reproduce the X-ray geometry. In addition, the binding energies of a dimer of 1 calculated by RIMP2 using the cc-pVDZ and cc-pVTZ corrected BSSE basis sets are -36.1 kJ/mol and -41.7 kJ/mol. The results suggest that complex 1 is significantly important for the attractive intermolecular interaction in 1.
																								



9.
An X-ray diffraction study of aqueous solutions of lutetium trichloride

O. V. Grechin1, P. R. Smirnov2, V. N. Trostin2
1Institute of Thermodynamics and Kinetics of Chemical Processes, Ivanovo State Chemical Technological University, Ivanovo
2G. A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo
Keywords: aqueous solutions of lanthanides, structure, X-ray diffraction analysis, small angle maxima of scattering intensity, radial distribution functions

Abstract >>
The X-ray diffraction analysis is used to study aqueous solutions of lutetium chloride in a wide concentration range under standard conditions. Small angle peaks on the functions of the X-ray scattering intensity and the maxima of radial distribution functions of the atomic-electron density are interpreted. It is found that highly concentrated solutions are characterized by a unique quasi-crystalline structure distinguished by short- and long-range ordering. Dilution of solutions results in that the own structure of the solvent starts to play the major role in the structure of the systems. It is established for the first time that small angle peaks on the scattering intensity functions are also manifested for diluted solutions, which indicates that long-range ordering is preserved in them.
																								



10.
SPECTROSCOPIC STUDY OF SOLVATION PROCESSES AND IONIC ASSOCIATION IN LITHIUM SALT SOLUTIONS WITH IONIC AND APROTIC SOLVENTS

M. M. Gafurov1, S. A. Kirillov2,3, K. Sh. Rabadanov1, M. B. Ataev1, D. O. Tretyakov2
1Analytical Center for Collective Use, Dagestan Scientific Center, Russian Academy of Sciences, Kh. I. Amirkhanov Institute of Physics, Makhachkala
2Joint Department of Electrochemical Energy Systems, National Academy of Sciences of Ukraine, Kiev
3Institute for Sorption and Problems Endoecology, National Academy of Sciences of Ukraine, Kiev
Keywords: Raman spectra, ionic liquid, ethylmethylimidazolinium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethylesulfonyl)imide, salvation

Abstract >>
The Raman spectra of the mixtures containing the low-temperature ionic liquid ethylmethylimidazolinium bis(trifluoromethanesulfonyl)imide (EMIIm), the salt component lithium bis(trifluoromethylesulfonyl)imide (LiIm), and the aprotic solvent ethylene carbonate (EC) are studied. It is found that the addition of the lithium salt to the ionic liquid results in the formation of ion pairs or more complex cation-anion aggregates. Dilution of these systems with ethylene carbonate leads to the solvation of lithium ions.
																								



11.
AMINO ACID HYDRATION IN AQUEOUS MAGNESIUM AND SODIUM SULFATE SOLUTIONS

V. P. Korolev, A. L. Serebryakova
G. A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: partial volume, amino acids, water-salt systems, group contributions, hydration numbers

Abstract >>
We study the partial volumes of amino acids in aqueous magnesium and sodium sulfate solutions, which have a different effect on the structure of water, and calculate the structural parameters of hydrated complexes of NH3+ and COO- groups: hydration numbers and water volumes inside and outside the hydration shell. The hydration numbers are given as a sum of the contributions of the interactions in the ternary (water-salt-amino acid) and binary (water-salt) systems.
																								



12.
CRYSTALLOGRAPHIC ANALYSIS OF NATURAL HEAVY METAL SULFIDES: ROUXELITE, FELBERTALITE, AND MARRUCCIITE

S. V. Borisov, S. A. Magarill, N. V. Pervukhina
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
Keywords: crystallographic analysis, structures of sulfides, cationic and anionic sublattices, rouxelite, felbertalite, marrucciite

Abstract >>
Crystallographic analysis of three complex sulfides with the C2/m symmetry (minerals rouxelite Cu2HgPb22Sb28S64(O,S)2, felbertalite Cu2Pb6Bi8S19, and marrucciite Hg3Pb16Sb18S46) established the fact of pseudotranslational ordering of both cations and separately anions by the families of crystallographic planes forming regular cationic and anionic sublattices respectively. One- and two-dimensional fragments of structures close in geometry to the PbS archetype are distinguished, which correlates with the conception of È. Makovicky’s school on the boxwork architecture of sulfosalts.
																								



13.
STRUCTURE OF THE MONOCLINIC MODIFICATION OF RE3B

A. P. Tyutyunnik1, T. V. Dyachkova1, Yu. G. Zaynulin1, S. A. Gromilov2,3
1Institute of Solid State Chemistry, Ural Division, Russian Academy of Sciences, Ekaterinburg
2A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
3Novosibirsk State University, Novosibirsk
Keywords: rhenium, borides, high pressure, high temperature, X-ray diffraction study, crystal chemistry

Abstract >>
By powder X-ray diffraction the structure of the monoclinic modification of Re3B is studied. The phase is obtained under high pressure and high temperature (10 GPa, 1800C) using nanocrystalline rhenium and amorphous boron. The results of the comparative crystal chemical analysis are reported.
																								



14.
CRYSTAL STRUCTURE AND LUMINESCENCE OF TWO CADMIUM 3,4,5-TRIMETHOXYLBENZOATE COMPLEXES

H. Chen, L. Zhang, B. Hu, X.-L. Wu, T. Wang, G. Huang, Y.-Q. Wang, C.-Z. Liu
China University of Geosciences, Wuhan, P. R. China
Keywords: 3, 4, 5-trimethoxylbenzoate, crystal structure, cadmium, spectral analysis, luminescence

Abstract >>
Two novel cadmium complexes with TMB (HTMB = 3,4,5-trimethoxybenzoic acid) are synthesized by the solution evaporation method. The structure and luminescent property of the two complexes are characterized by single crystal and powder X-ray diffraction, FT-IR spectroscopy, and photoluminescence emission spectra. Cd2(TMB)4(H2O)4·H2O (1) is a binuclear complex containing two Cd ions at a distance of 4.091 Å, both coordinated in octahedral geometry. Along the [100] direction, a 1D chain linked by intermolecular hydrogen bonds is formed. Cd(TMB)2(IM) (H2O)2 (2) is a mononuclear complex in which the Cd ion coordination can be described as a distorted pentagonal bipyramid, and weak hydrogen bonding interactions are present in its molecule. The fluorescent measurement shows that both complexes exhibit strong emission in the solid state at room temperature. Powder X-ray diffraction confirmed their crystallinity and purity.
																								



15.
STRUCTURE AND PHOTOLUMINESCENT PROPERTY OF A THREE-DIMENSIONAL PILLARED-LAYER La(III)-Cu(I) HETEROMETALLIC COORDINATION POLYMER

X. Li, H. Zhao, Q. Zeng
Zunyi Normal College, Zunyi, P. R. China
Keywords: heterometallic coordination polymer, crystal structure, pillared-layer, photoluminescent property

Abstract >>
A three-dimensional (3D) pillared-layer La(III)-Cu(I) heterometallic coordination polymer (HCP) formulated as [La2Cu4I3(Hina)7(H2O)]n ( 1) (Hina = isonicotinic acid), is synthesized by a hydrothermal reaction of La2O3, CuI, and ina. The crystal structure is determined by single crystal X-ray diffraction. HCP 1 crystallizes in the monoclinic space group P21/c with unit cell parameters: a = 17.0147(3) Å, b = 18.4431(3) Å, c = 16.7487(3) Å, β = 102.469(2)°, V = 5131.84(15) Å3, Z = 4. It features a 3D pillared-layer heterometallic organic framework, where Ln-ina layers are pillared by discrete [Cu8I6(ina)12] units along the direction of the a axis. In addition, the solid-state photoluminescent property is investigated.
																								



16.
IN VITRO ANTI-PROLIFERATIVE ACTIVITY OF NOVEL HEXACOORDINATED TRIPHENYLTIN(IV) TRIFLUOROACETATE CONTAINING A BIDENTATE N-DONOR LIGAND

M. Yousefi1, M. Safari1, M.B. Torbati1, A. Amanzadeh2
1Islamic Azad University, Shahr-e-Rey Branch, Tehran, Iran
2National Cell Bank of Iran, Pasteur Institute of Iran, Tehran, Iran
Keywords: organotin(IV) complex, 2,9-dimethyl-1,10-phenanthroline, spectroscopic study, anticancer drug, cell line

Abstract >>
The discovery of the antitumor activity of cisplatin led several research groups to investigate the possible therapeutic applications of other metal based compounds. In an attempt to develop novel metal based drugs with a different therapeutic profile to cisplatin, we have synthesized a new N,N-chelated organotin(IV) trifluoroacetate by the reaction of Ph<sub>3</sub>SnOCOCF<sub>3</sub> with equimolar amounts of 2,9-dimethyl-1,10-phenanthroline (Neocuproine). The complex is characterized by FT-IR and multinuclear NMR ( <sup>1</sup>H, <sup>13</sup>C, <sup>19</sup>F and <sup>119</sup>Sn). FT-IR results authenticate the ligand coordination to the organotin moiety via nitrogen atoms. Furthermore, the cytotoxic activity of the free ligand (Neocuproine) and triorganotin(IV) complex towards human cervix carcinoma HeLa, human myelogenous leukemia K562 and normal immunocompetent cells, peripheral blood mononuclear cells PBMC is evaluated by the MTT (3-[4,5-dimetylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) method. The complex exhibits higher activities than antitumor drug cisplatin in all the tested cell lines. These results indicate that the studied triorganotin(IV) complex can be a potential anticancer agent for further stages of screening <i>in vitro</i> and/or <i>in vivo</i>.
																								



17.
SYNTHESIS AND CRYSTAL STRUCTURE OF [La(NO3)3(H2O)2(BiPy)]·1.5(BiPy)

L. Alexandrescu1, P. Bourosh2, O. Oprea1, I. Jitaru1
1Polytechnical University of Bucharest, Bucharest, Romania
2Institute of Applied Physics, Academy of Sciences of Moldova, Chisinau, Moldova
Keywords: La(III) complex compound, synthesis, structure, crystal structure

Abstract >>
The molecular and crystal structure of the [La(NO3)3(H2O)2(2.2'-BiPy)]·1.5(2.2'-BiPy) compound is determined. The metal coordination polyhedron in the La(III) complex is formed from 10 donor atoms of O8N2: 6 oxygen atoms belong to three chelate-coordinated NO3¯ anions, 2 oxygen atoms belong to two water molecules, and 2 nitrogen atoms belong to a bidentate bipyridine molecule coordinated in the neutral form. The structure is based on the metal complexes linked together in chains through the O(W)-H⋯O hydrogen bonds, in which oxygen atoms of the coordinated NO3¯ anions act as acceptors. It is a framework structure, further stabilized by a system of O(W)-H⋯N and C-H⋯N hydrogen bonds, in which nitrogen atoms of the uncoordinated bipyridine molecules act as proton acceptors.
																								



18.
COMPLEX STRUCTURE Tri- AND POLYIODIDES OF IODOCYCLIZATION PRODUCTS OF 2-ALLYLTHIOQUINOLINE

E. V. Bartashevich1, I. D. Yushina1, E. A. Vershinina1, P. A. Slepukhin2, D. G. Kim1
1South Ural State University, Chelyabinsk, Russia
2I. Ya. Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Yekaterinburg, Russia
Keywords: triiodides, polyiodides, halocyclization, halogen bond, nonbonding interactions

Abstract >>
Iodocyclization products of 2-allylthioquinoline are obtained in the form of polyiodides with different stoichiometric compositions. X-ray crystallography data are analyzed for two different crystal structures of 1-iodomethyl-1,2-dihydro[1,3]thiazolo[3,2- ]quinolinium polyiodides: triiodide C12H11INS+I3¯ and complex polyiodide 2(C12H11INS+I3¯)·I 2. A comparison is made of the nonbonding interactions of dihydrothiazoloquinolinium with atoms of the triiodide anion and complex polyiodide to show the crystal structure features attributed to the participation of molecular iodine.
																								



19.
CRYSTAL AND MOLECULAR STRUCTURE OF IODOPROTATRANE: TRIS(2-HYDROXYETHYL)AMMONIUM IODIDE

M. G. Voronkov1, A. A. Korlyukov2, È. A. Zelbst3, V. S. Fundamenskii1, X. Borrmann4, D. E. Arkhipov2, Ya. V. Agapova1, T. A. Kochina1
1A. V. Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, St. Petersburg
2A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow
3East Siberian State Academy of Education, Irkutsk
4Max Planck Institute for the Chemical Physics of Solids, Dresden
Keywords: tris(2-hydroxyethyl)ammonium salts, iodoprotatrane, molecular structure, single crystal X-ray diffraction study

Abstract >>
By X-ray diffraction the crystal and molecular structure of iodoprotatrane ( tris(2-hydroxyethyl)ammonium iodide I[HN(CH2CH2OH)3]+ (IP) at 120 K and 293 K is determined. The IP cation, as in all protatranes, has the endo conformation. The N-H bond is surrounded by three CH2CH2OH groups. The stability of this configuration is explained by the intramolecular trifurcated inductive interaction with three oxygen atoms through the space of the nitrogen atom. In the IP crystal packing, each iodine anion is linked by three strong OH…I (2.63 Å) and three weak IH (3.13 Å) hydrogen bonds with six cations from the CH2N group. This indicates a greater nucleophilicity of the iodine atom.
																								



20.
CRYSTAL STRUCTURE OF CATENA-(2-THIO-BARBITURATO)DITHALLIUM(I)

N. N. Golovnev1, M. S. Molokeev2
1Siberian Federal University, Krasnoyarsk
2L.V. Kirensky Institute of Physics, Siberian Division, Russian Academy of Sciences, Krasnoyarsk
Keywords: crystal structure, catena-2-(thiobarbiturato)dithallium(I), hydrogen bonds, π-π interaction

Abstract >>
By powder X-ray diffraction the crystal structure of catena-(2-thiobarbiturato)dithallium (I) C4H2N2O2STl2 (C4H4N2O2S is 2-thiobarbituric acid, 2BA), Tl2TBA, is determined. Crystallographic data for Tl2TBA are as follows: a = 15.1039(3) Å, b = 12.0818(2) Å, c = 3.86455(6) Å, β = 97.203(1)°, V = 741.34(2) Å3, space group P21/n, Z = 4. There are two non-equivalent thallium atoms in the structure. The Tl1 polyhedron is a distorted trigonal prism due to the shortened Tl-S contact (3.634 Å), and the Tl2 polyhedron is a distorted square antiprism.
																								



21.
CRYSTAL STRUCTURE OF A Mn(II) COMPLEX WITH ISATIN-HYDRAZONE-S-BENZYLDITHIOCARBAZATE

J.-J. Xia
Anhui University of Architecture, Hefei, P. R. China
Keywords: X-ray diffraction, dithiocarbazate, isatin, manganese(II) acetate

Abstract >>
The reaction of Mn(OAc)2·4H2O with isatin-hydrazone-S-benzyldithiocarbazate (HIsa-SBn) results in the formation of a bis-ligand complex [Mn(Isa-SBn)2]2DMF. Its single crystal is obtained and the structure is determined by X-ray diffraction. It belongs to a monoclinic space group C2/c with the cell parameters: a = 23.290(4) Å, b = 11.4980(18) Å, c = 18.483(5) Å, V = 4087.6(14) Å3. The Mn(II) atom is six-coordinated with two amide O atoms, two azomethine N atoms, and two thiolate S atoms, resulting in a distorted octahedral geometry.
																								



22.
CRYSTAL STRUCTURES OF BIS(AZIDO)BIS(2-MORPHOLIN-4-YLETHYLAMINO)COPPER(II) AND BIS{2,4-DIBROMO-6-[(2-MORPHOLIN-4-YLETHYLIMINO)METHYL]PHENOLATO}COPPER(II)

H.-Y. Liu
Guangdong Pharmaceutical University, Zhongshan, P. R. China
Keywords: X-ray diffraction, copper complex, crystal structure, Schiff base, hydrogen bond

Abstract >>
Two new copper(II) complexes [Cu(MEA)2(N3)2] (1) and [Cu(BMP)2] (2), where MEA and BMP are 2-morpholin-4-ylethylamine and 2,4-dibromo-6-[(2-morpholin-4-ylethylimino)methyl]phenolate respectively, are prepared and characterized using elemental analysis, FT-IR spectroscopy, and X-ray single crystal diffraction. The crystal of 1 belongs to the triclinic system, space group P-1, with a = 6.661(2) Å, b = 8.440(3) Å, c = 8.913(3) Å, α = 102.032(3)°, β = 107.899(2), γ = 98.242(3), V = 454.6(3) Å3, Z = 1, Dc = 1.490 g/cm3, R1 = 0.0226, and wR2 = 0.0564. The crystal of 2 belongs to the monoclinic system, space group P21/c , with a = 7.0707(7) Å, b = 15.438(1) Å, c = 14.227(1) Å, b = 96.659(2), V = 1542.5(3) Å3, Z = 2, Dc = 1.821 g/cm3, R1 = 0.0437, and wR2 = 0.1041. In each complex, the Cu atom is in a square planar coordination. The molecules of 1 are linked through intermolecular N-H⋯N and N-H⋯O hydrogen bonds to form layers parallel to the ab plane. The molecules of 2 are linked through intermolecular C-H⋯Br hydrogen bonds to form a 3D network.
																								



23.
CRYSTAL STRUCTURE OF THE OCTAHEDRAL CLUSTER COMPLEX Trans-[{Re6S8}(pyz)4I2]·2pyz

M. A. Shestopalov, A. A. Ivanov, A. I. Smolentsev, Yu. V. Mironov
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
Keywords: rhenium, octahedral chalcogenide clusters, pyrazine, crystal structure

Abstract >>
The cluster complex of the composition trans-[{Re6S8}(pyz)4I2]·2pyz (pyz is pyrazine) is obtained by the reaction of Cs4[{Re6S8}I6] with molten pyrazine. The compound crystallizes in the triclinic space group P1 with the following unit cell parameters: a = 9.0562(7) Å, b = 10.2502(7) Å, c = 12.6783(9) Å, α = 98.537(3)°, β = 107.573(2), γ = 106.943(3), V = 1036.6(1) Å3, Z = 1, dcalc = 3.377 g/cm3. The crystal structure is built of trans- [{Re6S8}(pyz)4I2] cluster complexes and uncoordinated pyrazine molecules.
																								



24.
CRYSTAL STRUCTURE OF [Pd3(μ-OH)(μ-CH3COO)5]

V. V. Tatarchuk1, A. P. Sergievskaya1, N. V. Kuratieva1,2, I. V. Korolkov1, L. A. Sheludyakova1, S. A. Gromilov1,2
1A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
2Novosibirsk State University
Keywords: palladium, complex, single crystal X-ray diffraction study, crystal chemistry

Abstract >>
The crystals of the [Pd3(μ-OH)(μ-CH3COO)5] complex are obtained and characterized using powder and single crystal X-ray diffraction and IR spectroscopy. The crystal structure ( a = 15.6942(6) Å, b = 11.7190(3) Å, c = 9.7871(3) Å, V = 1800.05(10) Å3, space group Pna21, Z = 4) is formed from neutral trinuclear cyclic molecules of [Pd3(μ-OH)(μ-CH3COO)5], in which the OH group, together with five CH3COO anions, is a bridge ligand.
																								



25.
STRUCTURAL ANALYSIS OF ETHYL 2-Z-PHENYLHYDRAZONO-3-E-METHYLTHIO(THIOXO)METHYLHYDRAZONE-BUTANOATE

Ping Wu
Dezhou College, Universities of Shandong, Shandong, P. R. China
Keywords: X-ray diffraction, phenylhydrazono, methylhydrazono, butanoate

Abstract >>
A new compound of ethyl 2-Z-phenylhydrazono-3-E-methylthio(thioxo) methylhydrazone-butanoate is synthesized via the reaction between ethyl 2-Z-phenylhydrazono-3-oxo-butanoate and S-methyldithiocarbazate at room temperature. A single crystal of the titled compound is obtained and the structure is determined by X-ray diffraction. It belongs to a monoclinic P21 space group with the cell parameters: a = 5.335(1) Å, b = 15.907(4) Å, c = 9.507(2) Å, β = 90.21(1)°, V = 806.8(4) Å3. A one-dimensional parallel structure is constructed by an unclassic hydrogen bond and a weak π–π interaction.
																								



26.
MOLECULAR AND CRYSTAL STRUCTURE OF ETHYL-3(ALLYLAMINO)-9,9-DIMETHYL-7,11-DIOXO-1,5-DIPHENYLSPIRO [5.5]UNDEC-2-EN-2-CARBOXYLATE

A. M. Magerramov1, A. I. Ismiev1, K. A. Potekhin2, R. K. Askerov1
1Baku State University, Baku, Azerbaijan
2Vladimir State University, Vladimir, Russia
Keywords: , 1,3- , , multicomponent condensation, 1,3-dicarbonyl compounds, spirocycles

Abstract >>
New multicomponent condensation of dimedone, benzaldehyde, acetacetic ester, and allylamine in the 1:2:1:1 molar ratio respectively is revealed. It proceeds with the formation of ethyl-3(allylamino)-9,9-dimethyl-7,11-dioxo-1.5-diphenyl-spiro[5.5]undec-2-en-2-carboxylate whose crystal structure is determined by single crystal X-ray diffraction.
																								



27.
ENERGY PROPERTIES AND STRUCTURE OF 2AND 8-ALLYLTHIOQUINOLINE COMPLEXES WITH IODINE

E. V. Bartashevich1, E. A. Shmanina1, I. D. Yushina1, D. G. Kim2, V. G. Tsirelson3
1Chemistry Department, South Ural State University, Chelyabinsk, Russia
2Chemistry Department, South Ural State University
3D. I. Mendeleev University of Chemical Technology, Moscow, Russia
Keywords: , , , , halogen bonds, iodine, charge-transfer complexes, interaction energy

Abstract >>
The study focuses on the energy and quantum topological properties of substituted 2- and 8-allylthioquinoline complexes with iodine, which are assumed to correspond to prereaction states in the iodocyclization reaction leading to the formation of thiazolo- and tiazinoquinoline systems. The structures of the complexes and the corresponding atomic interactions are modeled considering the different conformational states of allyl-substituted quinolinethiols (thioquinolines). The energy values are analyzed for the interactions between the iodine molecule and different donor centers of the substituted quinoline system: the nitrogen heteroatom, sulfur, and p-system of the allyl group. It is shown that the formation of stable complexes with the nitrogen of the quinoline ring is complicated by steric hindrances posed by the S-allyl group at positions 2 and 8 of the quinoline system, which in turn contributes to the convergence of the cyclization centers.
																								



28.
"CRYSTAL" CONFORMATIONS OF 2-METHYL-2,4-PENTANEDIOL: DIPOLE MOMENT CALCULATIONS AND MOLECULAR STRUCTURE OPTIMIZATIONS

O. V. Grineva, T. M. Usacheva, V. I. Zhuravlev
Moscow State University, Moscow
Keywords: Cambridge Structural Database, quantum chemical calculations, intra- and intermolecular hydrogen bonds, aliphatic diols

Abstract >>
The structures of eight symmetrically independent molecules of 2-methyl-2,4-pentanediol (MPD) in six crystal substances are studied based on the data retrieved from the Cambridge Structural Database (CSD). Coordinates of the most part of hydrogen atoms in MPD molecules were not determined experimentally or not presented in CSD, however, O…O distances provide the conclusion about the formation of intramolecular hydrogen bonds in four molecules. To perform quantum chemical calculations the absent hydrogen atoms were added. The choice of H atomic positions in hydroxyl groups are based on the analysis of possible formation of intra- and intermolecular hydrogen bonds by MPD molecules in the respective crystals. The DFT method with the B3PW91 functional and the 6-31G(d,p) basis set is used to carry out for the first time: 1) the calculation of dipole moments and energies for MPD molecules in "crystal" conformations; 2) the optimization of the structure of these molecules with the calculation of dipole moments for the conformations corresponding to the local energy minima. It is found that among the molecules with the experimental geometric parameters one of the conformations without intramolecular hydrogen bonds is most favorable (μ = 0.56 D). As a result of the energy minimization of eight “crystal” conformations in vacuum, five energetically different conformers are obtained. Among them the conformer with the intramolecular hydrogen bond has the lowest energy (μ = 3.53 D). Four variants of the molecular structure correspond to it in the considered crystals, out of which two are R-enantiomers and two S-enantiomers.
																								



29.
SUPRAMOLECULAR HYDROGEL BASED ON L-CYSTEINE AND SILVER NANOPARTICLES

O. A. Baranova, S. D. Khizhnyak, P. M. Pakhomov
Tver State University, Tver, Russia
Keywords: supramolecular hydrogel, silver nanoparticles, L-cysteine

Abstract >>
A supramolecular hydrogel is synthesized on the basis of L-cysteine and silver nitrate with incorporated silver nanoparticles (SNPs), which are stabilized by L-cysteine. The steps in the synthesis and the structure and properties of the new system are investigated.
																								



30.
GEL FORMATION IN LOW-CONCENTRATION AQUEOUS SOLUTIONS CONTAINING N-ACETYL-L-CYSTEINE AND SILVER NITRATE

S. D. Khizhnyak1, M. M. Ovchinnikov2, P. M. Pakhomov1
1Tver State University, Tver, Russia
2Tver State Medical Academy, Tver, Russia
Keywords: N-acetyl-L-cysteine, silver nitrate, cluster, supramolecular structure, hydrogel

Abstract >>
The structurization process of a supramolecular system based on low-concentration aqueous solutions of N-acetyl-L-cysteine and silver nitrate is studied using electron spectroscopy, transmission electron microscopy, and dynamic light scattering. The mechanism of the gel formation in the system is considered.
																								



31.
ION-MOLECULAR INTERACTIONS IN THE METALLOPORPHYRIN-ACID SYSTEM IN LIQUID SOLUTIONS

T. N. Lomova1, M. E. Klyueva2, E. G. Mozhzhukhina1, E. Yu. Tyulyaeva1, N. G. Bichan1, S. V. Zaitseva1, S. A. Zdanovich1
1G. A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
2Ivanovo State Medical Academy, Ivanovo, Russia
Keywords: porphyrins, complexes, formation of H-associates, properties, structure

Abstract >>
A new form of MP…Hsolv+ metalloporphyrins is found and studied in the strong acid medium, the conditions of its formation and the qualitative reaction of its determination are established. It is shown that the same form has the H4TPP2+ dication (TPP is the 5,10,15,20-tetraphenyl-21H,23H-porphyrine dianion). The stability in different acid media and in the isolated state, spectral properties and the structure of H+-associates of porphyrins are analyzed in detail by UV-visible and 1H NMR spectroscopy and quantum chemical calculations. It is shown that they have a unique two-band visible electronic spectrum with the bands near 540 nm and 700 nm, which weakly depend on the type of the central atom in the complex and noticeably change when the chromophore is functionally substituted. The proton location the ion-molecular associate and the cases of the formation of H+-associates with higher stoichiometry are revealed.