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Journal of Structural Chemistry

2012 year, number 3

1.
first-principles STUDY OF THE CRYSTAL STRUCTURE AND EQUATION OF STATE OF NAPHTHALINE AND ANTHRACENE

Y. N. Zhuravlev, I. A. Fedorov, M. Y. Kiyamov
Keywords: naphthaline, anthracene, crystal structure, pressure, equation of state, bulk modulus, Gr?neisen parameter
Pages: 425-431

Abstract >>
A first - principles method of density functional theory with a gradient approximation of the exchange-correlation potential in the form of PBE implemented in the PWscf program of the Quantum ESPRESSO software using the Grimme′06 scheme is used to calculate the crystal structure of naphthaline and anthracene at a hydrostatic pressure ranging from 0 GPa to 2 GPa and from 0 GPa to 20 GPa respectively; their equations of states are analyzed. It is shown that under pressure the volume decreases due to voids, and the molecules themselves are practically not deformed. The Grüneisen parameter is calculated in the Slater-Dugdale-MacDonald-Zubarev-Vashchenko model. This parameter decreases from the equilibrium values of 2.356 (anthracene) and 3.226 (naphthaline) with an increase in the pressure. With the use of the Mie-Grüneisen equation under the additional Hugoniot-Renkin condition the impact pressure is calculated, which increases compared to the cold one at a relative compression V/V0, below 0.7.



2.
ELECTRON-NUCLEAR HAMILTONIAN for molecules with INTERNAL ROTATION

L. A. Gribov, N. I. Prokof'eva
Keywords: quantum theory of molecules, internal rotations, electron-nuclear Hamiltonian
Pages: 432-435

Abstract >>
A method to solve the problem of the electron-nuclear states of molecules with internal rotation and the smeared positions of nuclei due to this rotation is proposed. It is shown how to state the Hamiltonian for the description of the electron motion with regard to this smearing and the total electron-nuclear Hamiltonian.



3.
STRUCTURE AND INTRAMOLECULAR STABILIZATION OF GEOMETRIC ISOMERS OF Bi- AND TRITHIAZOLIDINE-4-ONES AND THEIR METHYL DERIVATIVES: A DFT AND QTAIM STUDY

G. V. Baryshnikov, B. F. Minaev, V. A. Minaeva, A. T. Baryshnikova
Keywords: density functional theory, Bader's method, geometric isomers, hydrogen bond
Pages: 436-442

Abstract >>
At the DFT level with the B3LYP hybride functional the structure and relative stability of geometric isomers of bi- and trithiazolidine-4-ones are calculated. Based on Bader's analysis of the electron density distribution the presence of intramolecular hydrogen bonds and van der Waals interactions is found in the studied isomers. Energies of these interactions are calculated. It is shown that the presence of a substituent in the thiazolidine ring affects the stabiliyty of the studied geometric isomers.



4.
BOND ENERGIES (Pt-NH3, Pt-Cl) AND PROTON AFFINITY OF CISPLATIN: A DENSITY FUNCTIONAL THEORY APPROACH

M. Juh??sz1, S. Takahashi1, S. Arulmozhiraja2, T. Fujii1
1 Department of Chemistry, Faculty of Sciences and Engineering, Meisei University
2 Research School of Chemistry, Australian National University
fujii@chem.meisei-u.ac.jp
Keywords: cis-diamminedichloroplatinum(II), bond strength, cation affinities, B3LYP density functional
Pages: 443-448

Abstract >>
The energies of the Pt-NH3 and Pt-Cl bonds of cisplatin are calculated by means of a density functional theory method with the B3LYP functional and various basis sets. The calculated bond energies of 37.38 kcalmol-1 and 64.35 kcalmol-1 for Pt-NH3 and Pt-Cl, respectively, agree well with the experimental values (37.28 kcalmol-1 and 69.31 kcalmol-1 respectively) derived from enthalpy changes. The proton and lithium ion affinities of cisplatin are also obtained with the B3LYP functional. Structural characterizations for the protonated and lithiated cisplatin complexes are given. Protonation and lithiation alter the geometric parameters, and the gas-phase proton affinity (198.71 kcalmol-1) is much higher than the lithium ion affinity (70.32 kcalmol-1).



5.
Prediction of Monomer Reactivity Parameters using quantum chemical descriptors

X.L. Yu1, Z.D. Tan2, X.Y. Wang3
1 College of Chemistry and Chemical Engineering, Hunan Institute of Engineering Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry
2 College of Chemistry and Chemical Engineering, Hunan Institute of Engineering
3 Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry
Keywords: artificial neural network, density functional theory, monomer, radical copolymerization, QSPR, quantum chemical descriptors
Pages: 449-544

Abstract >>
To construct artificial neural network (ANN) models for the prediction of reactivity parameters (u, v), density functional theory (DFT) calculations are carried out for 55 vinyl monomers, at the B3LYP level of theory with a 6-31G(d) basis set. After the generation of quantum chemical descriptors, the stepwise multiple linear regression (MLR) analysis and the ANN method are used to develop quantitative structure-property relationship (QSPR) models of parameters u and v. The ANN models produced test set root-mean-square (rms) errors of 0.35 for the parameter u and 0.34 for the parameter v. Research results indicate that the QSPR models based on DFT calculations and ANN techniques are accurate and possess the ability to generalize.



6.
BOND RUPTURE FORCE Measurement by means of a quartz resonator

F. N. Dultsev
Keywords: quartz crystal microbalance, bond rupture force
Pages: 455-465

Abstract >>
Methods to measure the bond rupture force are considered. It is proposed to use a quartz resonator as an active element rather than simply a sensor. When the surface oscillation amplitude of an AT quartz resonator increases smoothly (rupture event scanning), a particle attached to the quartz surface is removed by inertial forces, and from their values it is easy to obtain the bond dissociation value. This procedure provides reliable measurements of the rupture force of about 10 pN. As the atomic force microscopy method, the rupture event scanning does not apply electromagnetic radiation, but has simpler instrumental set-up. The scanning requires minimum sample preparation, can be performed in various media (vacuum, air, liquid), and takes only a few minutes.



7.
N,N′-DIPYRIDOXYL(ETHYLENEDIAMINE) SCHIFF-BASE LIGAND AND ITS SQUARE-PYRAMIDAL COPPER(II) COMPLEX: SYNTHESIS, EXPERIMENTAL AND THEORETICAL CHARACTERIZATION

S.A. Beyramabadi1, A. Morsali1, S.H. Vahidi1, M.J. Khoshkholgh2, A.A. Esmaeili2
1 Department of Chemistry, Mashhad Branch, Islamic Azad University
2 Department of Chemistry, Faculty of Science, Birjand University
beiramabadi@yahoo.com
Keywords: DFT, IR assignment, NMR, Schiff base, salen, copper(II)
Pages: 466-473

Abstract >>
A new tetradentate N,N′-dipyridoxyl(1,2-ethylenediamine) [=H2ES] Schiff-base ligand and its Cu(II) salen complex [Cu(ES)(H2O)] are synthesized and characterized by IR, UV-Vis, 1H NMR, mass spectrometry, and elemental analysis. Their optimized geometries and theoretical vibrational frequencies are computed by using the density functional theory method where the B3LYP functional was used. Also, the 1H NMR chemical shifts of the H2ES ligand are calculated at the same computational level. In the optimized structure of the free ligand, two pyridine rings are not in the same plane. In the structure of the complex, the Schiff-base ligand acts as a dianionic tetradentate ligand in the N,N,O-,O- manner, so that the coordinating atoms occupy equatorial positions. The H2O ligand occupies the axial position of the square-pyramidal complex. The calculated results are consistent with the experimental ones, confirming the suitability of the optimized structures for the H2ES ligand and its Cu(II) complex.



8.
PSEUDOPOTENTIAL CALCULATION OF THE STRUCTURE AND THERMODYNAMICS OF LIQUID ALKALI METALS WITH A SQUARE-WELL MODEL AS A REFERENCE SYSTEM

N. . Dubinin, A. A. Yuryev, N. A. Vatolin
Keywords: liquid metal, reference system, pseudopotential, pair interatomic interaction, variational method, structure factor, thermodynamic properties
Pages: 474-481

Abstract >>
We investigate the applicability of a variational method with a new reference system (square-well model) to the description of the structure and thermodynamics of liquid metals. An expression for the system entropy for a one-component fluid is derived. The three parameters of the model (the hard-sphere diameter and the width and depth of the square well) are determined by the variational method using the local pseudopotential approximation. The approach is used for liquid Na and K, and the calculated results are compared with experiment. It is shown that the approach can provide a realistic description of the properties of liquid metals.



9.
Thermodynamic perturbation theory of simple LIQUIDS: MONTE CARLO SIMULATION of a hard sphere system and the Helmholtz free energy of SW FLUIDS

Y. T. Pavlyukhin
Keywords: simple liquids, thermodynamic perturbation theory, WCA theory of simple liquids, SW fluid, hard sphere fluid
Pages: 482-492

Abstract >>
The Monte Carlo method is used to simulate similar sized hard sphere systems in a wide range of densities (from η 0.005 to 0.530 with a step of η = 0.005). The models are used to calculate the coefficients of the thermodynamic perturbation theory series for SW fluids up to the fourth order. The width of the attraction zone of the SW potential λ is varied from 1 to 2.5 sphere diameters. The analytical expressions approximating the obtained coefficients by polynomials with respect to the variables η and λ are determined. The absolute accuracy of the approximation is estimated to be better than 0.001. All the necessary data for the calculation of the Helmholtz free energy of SW fluids up to the fourth-order perturbation theory are given.



10.
EFFECTS OF ELECTROLYTE CONCENTRATION, TEMPERATURE, AND PRESSURE ON THE SECHENOV SALT-EFFECT PARAMETER: He-NaCl-H2O SYSTEM

V. K. Abrosimov, E. Y. Lebedeva
Keywords: helium, water, aqueous solutions of sodium chloride, solubility, temperature and pressure effects, Sechenov parameters, pairwise interaction parameters
Pages: 492-500

Abstract >>
The data on the solubility of helium in water and aqueous solutions of sodium chloride at a temperature of T = 293-353 K and a He partial pressure of p2 = 0.1-20 MPa are used to calculate the standard parameters of the Sechenov salt effect and estimate, within the formalism of the McMillan-Mayer theory, the parameters of the pairwise solute-solute interaction.



11.
STRUCTURE OF HETEROASSOCIATES FORMED IN THE HF-(CH3)2CO BINARY LIQUID SYSTEM

E. G. Tarakanova, G. V. Yukhnevich
Keywords: binary liquid system, IR spectrum, quantum chemical calculation, hydrogen bond, heteroassociates, hydrogen fluoride, acetone
Pages: 501-507

Abstract >>
The vibrational spectra of a series of HF solutions in acetone (1:20-8.9:1) are analyzed with the help of special techniques. It is shown that three types of strong heteroassociates (HAs) with 1:1, 4:1, and ≥10:1 stoichiometric ratios of the molecules are formed in the HF-(CH3)2CO binary liquid system. The concentration ranges of the existence of HAs in the solution and the stretching vibrational frequency of their constituent HF molecules are estimated. The density functional method (B3LYP/6-31++G(d,p)) is used to calculate the optimal configurations and IR spectra of the (HF)m((CH3)2CO)n molecular complexes (m = 1, 2, 4, 8, n = 1, 2) of different structure. The relative stability of the latter is studied. By comparing the calculated and experimental data, the composition (2:2 and 4:1) and structure of two types of HAs are determined.



12.
structure of complex salts [Co(NH3)6][Rh(NO2)6] and [Co(NH3)6][(NO2)3Rh(μ-NO2)1+x(μ-OH)2-xRh(NO2)3](2-x)(H2O), x = 0.17

A. I. Gubanov, N. V. Kuratieva, E. Y. Filatov, S. V. Korenev
Keywords: rhodium, cobalt, complex salt, single crystal, powder X-ray diffraction study, coordination ion stabilization
Pages: 508-514

Abstract >>
The structures of two salts [Co(NH3)6][Rh(NO2)6] (I) and [Co(NH3)6][(NO2)3Rh(μ-NO2)1+x(μ-OH)2-x Rh(NO2)3](2-x)(H2O), x = 0.17 (II) are solved. Single crystals of the salts are obtained by the counter diffusion method through the gel of aqueous solutions of [Co(NH3)6]Cl3 and Na3[Rh(NO2)6]. The structure of [Co(NH3)6][Rh(NO2)6] is consistent with the diffraction data for a polycrystalline sample of poorly soluble fine salt formed in the exchange reaction between aqueous solutions of [Co(NH3)6]Cl3 and Na3[Rh(NO2)6]. The structure of [Co(NH3)6][(NO2)3Rh(μ-NO2)1+x(μ-OH)2-xRh(NO2)3](2-x)(H2O), x = 0.17 exhibits the stabilizing effect of a large cation in the formation of novel, unknown previously coordination ions: [(NO2)3Rh(μ-NO2)(μ-OH)2Rh(NO2)3]3- and [(NO2)3Rh(μ-NO2)2(μ-OH)Rh(NO2)3]3-.



13.
STRUCTURE AND CHARACTERIZATION OF A 1D DOUBLE CHAIN COPPER (II) COMPLEX {[Cu(BIX)2(H2O)2](PhCOO)2}n

G.-H. Cui, J.-C. Geng, T.-F. Liu, X. Peng, C.-H. He, C.-H. Jiao
College of Chemical Engineering, Hebei United University
tscghua@126.com
Keywords: 1, 4-bis(imidazole-1-methyl)benzene, benzoate, coordination polymers, copper complex
Pages: 515-519

Abstract >>
A novel copper(II) complex {[Cu(BIX)2(H2O)2](PhCOO)2}n (1) (BIX = 1,4-bis(imidazole-1-methyl))benzene) is synthesized and characterized by elemental analysis, IR, TG, and single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic crystal system with the P-1 space group, Z = 1, a = 9.465(2) Å, b = 9.703(2) Å, c = 12.060(2) Å, α = 77.26(3), β = 70.37(3), γ = 67.14(3), and V = 956.1(3) Å3. The crystal structural analysis of complex 1 shows that the copper center is six-coordinated in an elongated octahedral geometry by four N atoms from four different BIX and two O atoms from two water molecules; two neighboring Cu(II) cations are bridged by two BIX extending into an infinite 1D double chain structure.



14.
crystal structures of [Pd(En)2](ReO4)2, [Pd(En)2](NO3)2, AND [PdL2](ReO4)2 (L: N,N′-DIISO-PROPYLIDENEETHANE-1,2-DIAMINE)

S. P. Khranenko, E. A. Bykova, A. V. Alexeyev, S. A. Gromilov
Keywords: palladium, rhenium, ethylenediamine, nitrate, crystal chemistry, single crystal X-ray diffraction study
Pages: 520-526

Abstract >>
At T = 150 K, the crystal structures of [Pd(En)2](ReO4)2, [Pd(En)2](NO3)2, and [PdL2](ReO4)2 (L is N,N′-diisopropylideneethane-1,2-diamine) are studied. Crystal chemical analysis is performed, and the main factors affecting the packing of fragments in these structures are determined.



15.
COMPLEX SALTS WITH PARTICIPATION OF [Rh(NH3)6]3+ CATIONS

S. P. Khranenko, E. A. Bykova, A. V. Alexeyev, A. P. Tyutyunnik, S. A. Gromilov
Keywords: rhodium, rhenium, molybdenum, tungsten, complex salt, crystal chemistry, single crystal X-ray diffraction study
Pages: 527-533

Abstract >>
Four complex salts with the polyatomic [Rh(NH3)6]3+ cation are synthesized and studied by X-ray diffraction. The crystallographic characteristics of [Rh(NH3)6](WO4)Cl are determined and the structures of [Rh(NH3)6]Cl3, [Rh(NH3)6](ReO4)32H2O, and [Rh(NH3)6](MoO4)Cl3H2O are solved. The features of mutual packing of the fragments are studied.



16.
DOUBLE COMPLEX SALTS [Pd(NH3)4]3[Rh(NO2)6]2, [Pd(NH3)4]3[Rh(NO2)6]2H2O AS PROMISING PRECURSORS TO PREPARE Pd-Rh NANOALLOYS

A. A. Rybinskaya, P. E. Plyusnin, E. A. Bykova, S. A. Gromilov, Y. V. Shubin, S. V. Korenev
Keywords: rhodium, palladium, double complex salts, single crystal X-ray diffraction study, thermal analysis, nanoalloy
Pages: 534-539

Abstract >>
Two new double complex salts [Pd(NH3)4]3[Rh(NO2)6]2 (I) and [Pd(NH3)4]3[Rh(NO2)6]2H2O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) Å, V = 6767.4 Å3, F-43c space group, Z = 8, dx = 2.548 g/cm3; II: a = 21.160(6) Å, b = 8.085(7) Å, c = 21.363(4) Å, β = 91.71(4), V = 3661.1(6) Å3, P21/c space group, dx = 2.357 g/cm3. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd0.59Rh0.41 (Fm-3m space group, a = 3.856(2) Å, crystallite size of 8-11 nm).



17.
MOLECULAR STRUCTURE, QUANTUM CHEMICAL INVESTIGATION, AND THERMAL BEHAVIOR OF (DNAZ-CO)2

H.X. Ma1, N.N. Zhao1, B. Yan2, Y.L. Guan1, J.F. Li1, J.R. Song3
1 College of Chemical Engineering, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest Univer- sity
2 College of Chemical Engineering, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest Univer- sity School of Chemistry and Chemical Engineering, Yulin University
3 College of Chemical Engineering, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, Northwest Univer- sity Conservation Technology Department, the Palace Museum
mahx@nwu.edu.cn
Keywords: bis-(3, 3-dinitroazetidinyl)-oxamide ((DNAZ-CO)2), molecular structure, quantum chemical investigation, thermal behavior
Pages: 540-547

Abstract >>
Bis-(3,3-dinitroazetidinyl)-oxamide ((DNAZ-CO)2) is an acyl derivative of 3,3-dinitroazetidine (DNAZ). It is prepared and its crystal structure is determined. The crystal is orthorhombic, Fdd2 space group, a = 13.136(14) Å, b = 19.48(3) Å, c = 10.326(14) Å, V = 2642 (6) Å3, Z = 8. A density functional theory (DFT) method of the Amsterdam Density Functional (ADF) package is used to calculate the geometry, frequencies, and properties. The optimized geometry, frontier orbital energy, and main atomic orbital percentage are obtained. The thermal behavior is studied under a non-isothermal condition by DSC and TG/DTG methods. The apparent activation energy (Ea) and pre-exponential factor (A) of the exothermic decomposition reaction of (DNAZ-CO)2 are 164.10 kJmol-1 and 1013.38 s-1 respectively. The critical temperature of thermal explosion is 272.20 C. The values of ΔS, ΔH, and ΔGof this reaction are 6.44 Jmol-1K-1, 163.76 kJmol-1 and 160.34 kJmol-1 respectively.



18.
CRYSTAL STRUCTURE OF SALTS OF INDOLE ALKALOID NORFLUOROCURARINE

B. Tashkhodzhaev, M. M. Mirzaeva, P. K. Yuldashev
Keywords: indole alkaloid, norfluorocurarine, salt forms, X-ray crystallography
Pages: 548-553

Abstract >>
Single crystal XRD is used to study the crystals of salts of indole alkaloid norfluorocurarine: hydrochloride recrystallized from absolute alcohol, dihydrate hydrochloride recrystallized from water, methochloride monohydrate recrystallized from water, solvate form of methochloride obtained from ethanol, and methobromide monohydrate. Intra- and intermolecular hydrogen bonds are analyzed in these crystals. The crystal structures of norfluorocurarine methochloride and methobromide monohydrates are isomorphic. In norfluorocurarine salts, the orientation of the carbonyl group is determined by the intramolecular 19=΅H-N1 hydrogen bond that is absent in the solvate form with ethanol.



19.
PHASE COMPOSITION AND STRUCTURE OF NANOCRYSTALLINE PRODUCTS OF SOLID-PHASE OXIDATIVE THERMOLYSIS OF IRON OXALATE DIHYDRATE

D. A. Yatsenko, V. P. Pakharukova, S. V. Tsybulya, A. A. Matvienko, A. A. Sidel'nikov
Keywords: powder X-ray diffraction, structural studies, modeling, iron oxides, nanopowders, Debye formula, radial distribution function
Pages: 554-562

Abstract >>
X-ray diffraction studies of the ultradisperse products of the solid-phase oxidative thermolysis of iron oxalate dehydrate are performed. Models are considered and diffraction patterns are calculated for the nanopowders of different crystalline modifications of iron oxide. Calculations are performed for the particles of various shapes and sizes, starting from one unit cell. Despite that the final product is the hematite phase, the reaction is shown to pass through the formation of particles with the ferrihydrite structure.



20.
STRUCTURE AND MICROSTRUCTURE OF NANO- CRYSTALLINE SAMPLES OF THE COMPOSITION Re0.65Pt0.35

E. A. Bykova, A. V. Zadesenets, T. V. D'yachkova, E. Y. Gerasimov, S. A. Gromilov
Keywords: rhenium, platinum, nanosized particles, complex salt, X-ray diffraction, crystal chemistry
Pages: 563-568

Abstract >>
Alloys of the composition Re0.65Pt0.35 are prepared by thermal reduction of a bimetallic complex salt (NH4)2[ReCl6]0.65[PtCl6]0.35 in the hydrogen atmosphere and also by thermal-baric treatment of a mixture of nanosized powders of rhenium and platinum. The products are examined by powder X-ray diffraction and HRTEM. The compositions of the obtained phases are estimated using EDS and crystal chemical analysis of phases known for the Re-Pt system.



21.
STRUCTURE OF MOLECULAR NANOPARTICLES OF PETROLEUM ASPHALTENES

M. Y. Dolomatov, S. A. Shutkova, S. V. Dezortsev
Keywords: petroleum asphaltenes, nanoparticles, non-planar cup-like structure, asphaltene molecules
Pages: 569-573

Abstract >>
Ab initio RHF/3-21G** and + molecular mechanics method are employed to calculate the structural chemical parameters of molecular nanoparticles of petroleum asphaltenes. It is found that naphtheno-aromatic rings have a non-planar cup-like character. The values of dihedral angles α1 between the planes of aromatic and naphthene rings, which are calculated by the RHF/3-21G** method, are within 156-163. The values of dihedral angles α2, which were calculated by the molecular mechanics method, are within 156-164.



22.
SUPRAMOLECULAR ARCHITECTURE OF A 1:1 COMPLEX OF PYROGALLOL WITH DIMETHYLSULFOXIDE

T. M. Polyanskaya, A. I. Smolentsev
Keywords: pyrogallol, dimethylsulfoxide, structure, single crystal, molecular complex, intermolecular interaction, hydrogen bond
Pages: 574-579

Abstract >>
The crystal structure is solved for a 1:1 molecular complex of pyrogallol and dimethylsulfoxide. Crystal dat a: C8H12O4S, M = 204.24, orthorhombic, Pna21 space group; unit cell parameters: a = 10.9620(4) , b = 10.9542(4) , c = 8.0561(3) , V = 967.38(6) 3, Z = 4, dx = 1.402 g/cm3, R1 = 0.0216, T = 150 K. The molecules are joined in a supramolecular ensemble by O-HO and C-H hydrogen bonds.



23.
THEORETICAL STUDY ON THE MOLECULAR ELECTRONIC PROPERTIES OF SALICYLIC ACID DERIVATIVES AS ANTI- INFLAMMATORY DRUGS

E. Mousavinezhad sarasia1, M.E.S. Soliman2, B. Honarparvar3
1 Department of Biochemistry, Payame Noor University
2 School of Pharmacy and Pharmacology, University of KwaZulu Natal
3 School of Chemistry, University of KwaZulu Natal
Honarparvar@ukzn.ac.za bahareh_honarparvar@yahoo.com
Keywords: salicylamide (SAM), gentisamide (GAM), HOMO-LUMO band gap, excitation energies, ab initio
Pages: 580-587

Abstract >>
A systematic computational study was carried out to determine the structural stability of salicylic acid derivatives as well as the acidic properties of the protonation-deprotonation site and excitation parameters of the considered drugs at different temperatures using quantum chemical calculations. For further structural information, the dipole moment and differences in the energy of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) as Δ(HOMO-LUMO) were compared. A high stability of the salicylic acid derivatives was referred to the large HOMO-LUMO band gap. The result of the current study may give useful information about the drug biochemical functionality based on the physical and chemical nature at different temperatures, and in this way the study on the structural features of analogous molecules of salicylic acid derivatives with higher drug functionality would be possible.



24.
A COMPUTATIONAL EVALUATION OF THE STRUCTURE AND HEAT OF FORMATION OF HALOTRIFLUOROMETHYLSULFANE COMPOUNDS XC(O)SCF3 (X = F and Cl)

C. Buend??a-atencio
INIFTA, Facultad de Ciencias Exactas, Universidad Nacional de La Plata Grupo de Qumica Cuntica y Terica, Facultad de Ciencias Exactas y Naturales, Universidad de Cartagena
cbuendia92@inifta.unlp.edu.ar
Keywords: halotrifluoromethylsulfane, quantum chemistry, ab initio calculations, geometric structure, enthalpies of formation
Pages: 588-592

Abstract >>
Enthalpies of formation ((g)) are calculated for syn and anti conformers of FC(O)SCF3 and ClC(O)SCF3 using the atomization methods with the Gaussian-n composite methods for which experimental values do not exist. DFT approaches and MP2 methods are employed to optimize the molecular geometries of XC(O)SCF3 (X = F and Cl). Excellent results are obtained with the reported experimental data.



25.
Re-DETERMINATION OF the CRYSTAL STRUCTURE OF heyrovskyite MINERAL Pb6Bi2S9 (KUDRYAVYI volcano, ITURUP ISLAND, Kurils, RUSSIA)

N. V. Pervukhina, S. V. Borisov, S. A. Magarill, N. V. Kuratieva, N. N. Mozgova, I. V. Chaplygin
Keywords: heyrovskyite, Pb-Bi sulfosalts, tablet structures, isomorphism Pb/Bi, crystal structure
Pages: 593-597

Abstract >>
Heyrovskyite mineral Pb6Bi2S9 from fumarole exhalations of the Kudryavyi volcano (Iturup island, Kurils, Russia) is studied by X-ray crystallography (Bruker Nonius X8 Apex with a 4K CCD detector, R = 0.0405). Unit cell parameters are: a = 4.1457(1) Å, b = 13.7421(5) Å, c = 31.5005(12) Å, V = 1794.6(1) Å3, Z = 4, dx = 7.216 g/cm3, Cmcm space group, R=0.0405. The resulted structure is similar to the known structures of heyrovskyites from other deposits with some variation in the cation composition.



26.
X-RAY STUDY OF THE THIRD POLYMORPHIC STRUCTURE OF μ-OXO-BIS[(OCTAETHYLPORPHINATO) IRON(III)]: [(OEPFe)2O)]

M. Khorasani-motlagh1, M. Noroozifar1, J. Saffari1, B.O. Patrick2
1 Chemistry Department, University of Sistan & Baluchestan
2 Chemistry Department, University of British Columbia
mkhorasani@chem.usb.ac.ir
Keywords: heme, iron(III), octaethylporphyrin, oxo-dimer, crystal structure
Pages: 598-602

Abstract >>
Exposure of dichloromethane solution of [OEPFeIIICl], where OEP is the dianion of octaethylporphyrin, to dioxygen results in its transformation into the -oxo bridged compound [(OEPFe)2O)]. The structure of [(OEPFe)2O)] is determined by X-ray diffraction analysis. It contains binuclear centrosymmetric [(OEPFe)2O]. The Fe atom is five-coordinated to four N atoms of the porphyrin ring and to one bridging O atom. The compound is characterized by an average Fe-N bond length of 2.096 . The Fe-O bond distance is 1.7739(12) , the Fe-O-Fe bond angle is 180.0 and the two porphyrin rings are parallel. Crystal dat a: triclinic crystal system, a = 10.915(4), b = 12.951(4), c = 13.403(4) , = 118.06(1), = 100.33(1), = 102.43, P space group, V = 1144.5(1) 3, Z = 1.



27.
CRYSTAL STRUCTURE OF A NEW MONONUCLEAR COMPLEX OF Mn(II) WITH A bbbi LIGAND (bbbi = 1,4-bis(benzimidazol-1-yl)-2-butene)

G.-H. Cui, T.-F. Liu, C.-H. He, C.-H. Jiao
College of Chemical Engineering, Hebei United University
tscghua@126.com
Keywords: bis(benzimidazole), hydrogen bond, manganese(II), mononuclear complex
Pages: 603-607

Abstract >>
A new mononuclear complex Mn(bbbi)2(H2O)4(ClO4)2(bbbi)2(H2O)2 1 (bbbi = 1,4-bis(benzimidazol-1-yl)-2-butene) is synthesized under hydrothermal conditions and characterized by IR spectroscopy, elemental analysis, and single crystal X-ray structural analysis. Crystal data for 1: triclinic, P, a = 8.8478(7) Å, b = 15.0550(11) Å, c = 16.4310(12) Å, α = 108.657(7), β = 104.044(7), γ = 99.317(7), V = 1942.2(3) Å3, Z = 1, final R = 0.0621. Each manganese atom is octahedrally coordinated by four aqua ligands and two nitrogen atoms of two distinct bbbi ligands. The molecule is stabilized by hydrogen bonding and π⋯π interactions.



28.
CRYSTAL STRUCTURE OF BIS[2-((E)-(P-TOLYLIMINO) METHYL)-6-BROMO-4-CHLOROPHENOL]COPPER(II)

X.H. Pu
Department of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences
pxh913@163.com
Keywords: copper(II) complexes, single crystal X-ray analysis
Pages: 608-610

Abstract >>
A new complex CuL2 1 [HL = 2-((E)-(p-tolylimino) methyl)-6-bromo-4-chlorophenol] is obtained and characterized using the single crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, P21/c space group, with a = 13.3203(13), b = 12.3052(11), c = 17.8664(17) Å, β = 105.3420(10), V = 2824.1(5) Å3, Z = 4, Dc = 1.672 g/cm3, R1 = 0.0686. The geometry around copper(II) is intermediate between square planar and tetrahedral. The units of the complex are linked via weak inter-molecular BrBr contracts, leading to the formation of one-dimension (1D) chains along the b axis; the multipoint CuCl intermolecular interactions extend the 1D chain into a 2D layer.



29.
NANOPOROUS solvate of N,N-phthaloyl-glycine

N. A. Tumanov, N. A. Pankrushina, A. A. Nefedov, E. V. Boldyreva
Keywords: nanoporous solvate of N, N-phthaloyl-glycine, crystal structure, thermogravimetry, high-resolution mass spectrometry
Pages: 611-614

Abstract >>
N,N-phthaloyl-glycine is synthesized under microwave activation without solvent. Its nanoporous solvate is obtained by recrystallization. The solvate is studied by single crystal and powder XRD, thermogravimetry, and mass spectrometry. The crystals are composed of dimers that form a framework structure with infinite channels of about 4 Å in diameter, containing a non-stoichiometric amount of chloroform (the mole fraction is close to 0.35). The nature of the incorporated solvate molecules is determined by high-resolution mass spectrometry, and their quantity is found by thermogravimetry.



30.
crystal structure of nickel(II) Bis-(1,1,1,- TRIFLUORO-5,5-DIMETHYL-2,4-hexanedionate)-1,3-diaminopropane

S. I. Dorovskikh, D. A. Piryzev, A. I. Smolentsev, N. B. Morozova
Keywords: octahedral complex of nickel(II), ?-diketonate derivatives, single crystal X-ray diffraction study
Pages: 615-618

Abstract >>
The structure of the complex of nickel(II) bis-(1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate) with 1,3-diaminopropane is determined by single crystal X-ray diffraction at a temperature of 150 K. Crystallographic data for C20H34F6N2NiO5: a = 17.5446(8) Å, b = 18.1171(10) Å, c = 18.6654(7) Å, β =
115.4150(10), space group C2/c, V = 5358.8(4) Å3, Z = 8, dcalc = 1.376 g/cm3, R = 0.0435. The structure is molecular; the metal atom coordinates four oxygen atoms of two β-diketonate ligands and two nitrogen atoms of propylenediamine. In the crystal, the molecules are bonded only by van der Vaals interactions.



31.
CRYSTAL AND MOLECULAR STRUCTURE OF THE COMPLEX OF N-(1-SILATRANYLMETHYL)-3,5-DIMETHYLPYRAZOLE WITH COBALT DICHLORIDE

M. G. Voronkov, . A. Zel'bst, A. D. Vasiliev, A. S. Soldatenko, Y. I. Bolgova, O. M. Trofimova
Keywords: N-(1-silatranylmethyl)-3, 5-dimethylpyrazole, cobalt dichloride, molecular structure, single crystal X-ray diffraction
Pages: 619-622

Abstract >>
X-ray diffraction is used to determine the crystal and molecular structure of the complex of N-(1-silatranylmethyl)-3,5-dimethylpyrazole with cobalt dichloride (I). This is yet another example of the participation of the endocyclic oxygen atom of the silatrane fragment in complexation with a metal atom. Metal dichloride interconnects two heterocyclic systems of dimethylpyrazole (DMP) and silatrane (Sa). The coordination polyhedron of the cobalt atom is a tetrahedron.