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Journal of Structural Chemistry

2013 year, number 1

1.
ZERO FIELD SPLITTING OF TRIPLET LEVELS OF CONJUGATED MOLECULES: A COMPARISON OF EXACT AND APPROXIMATE p-SCHEMES

A. V. Luzanov
Keywords: FCI, CIS, and ROHF methods, D parameter, spin-orbit coupling anisotropy, aromatic systems

Abstract >>
An exact method (full configuration interaction) and approximate schemes for the calculation of the anisotropy spin coupling matrix and the corresponding zero field splitting D parameter are considered. Calculation algorithms for the exact method and a special case (valence bond (VB) method) are also presented. The results of specific π calculations give evidence that the VB method in fact cannot be recommended for the description of the spin-spin interaction, especially for biradicals with the triplet ground state. At the same time, the Tamm–Dancoff method (taking into account all singly excited configurations) provides on average a good approximation to an accurate description of non-degenerate triplet states. The description of fine spin effects, which is rougher, but better than that in VB, is given by the restricted HartreeFock method for open shells.



2.
STRUCTURE OF THE HOO–N=NOOH INTERMEDIATE IN HYDROGEN PEROXIDE ACTIVATION OF N2: QUANTUM CHEMICAL DFT CALCULATIONS

I. I. Zakharov, M. G. Loriya, A. B. Tselishchev
Keywords: density functional theory (DFT) method, and 2 high energy states, activation of N2, molecular and spectroscopic parameters, HOON=NOOH intermediate, hydroxyl radical spillover

Abstract >>
Quantum chemical calculations of the electronic and geometric structure of the HOO–N=NOOH intermediate in the activation reaction of molecular nitrogen are performed by the density functional theory method at the B3LYP/6-311++G(3df,3pd) level. For HOO*N=N*OOH isotopomers with respect to nitrogen the spectroscopic parameters of the intermediate are characterized, which indicate the possibility of its experimental detection. The reactivity of the high energy state * (2A') in the activation of N2 is analyzed. The possibility of the generation of singlet oxygen 2(1Δg ) is considered in the dimerization of radicals with the ground state (2A") followed by the sensitization of excited * (2A'). A substantiated process of bonding of molecular nitrogen is given as an example of the self-organization of a chemical system in the activation of a hard-to-oxidize N2 substance.



3.
A QUANTUM CHEMICAL STUDY OF THE MECHANISM OF THE REGIOSELECTIVE DOMINO-REACTION OF O-VINYL-2-TETRALONE OXIME

V. A. Shagun, A. M. Vasil’tsov, A. V. Ivanov, A. I. Mikhaleva, B. A. Trofimov
Keywords: O-vinyl oxime, indole, quantum chemical calculation, reaction mechanism, sin-(Z)/anti-(E)-isomerization

Abstract >>
Quantum chemical (DFT) methods are used to study the mechanisms of intramolecular rearrangements (domino-transformations) in O-vinyl-2-tetralone oxime, which potentially can produce both conjugated and non-conjugated dihydrobenzindoles. Transition states of elementary reaction steps are localized. The 1,3-prototropic shift promoted by a mediator molecule (2) is the limiting step. An activation barrier of the formation of conjugated indole is 4.14 kcal/mol lower than the formation channel on the non-conjugated analog. Activation barriers of syn-(Z)/anti-(E)-isomerization in O-vinyl-2-tetralone oxime are analyzed. It is shown that with regard to barriers of the promoted prototropic shift, Z/E-isomerization is a rapid process.



4.
INVESTIGATION OF EPR PARAMETERS AND THE LOCAL STRUCTURE OF THE RHOMBIC Cu2+ CENTER IN ZINC FLUORIDE

H.-M. Zhang, X. Wan
Keywords: electron paramagnetic resonance, defect structure, Cu2+, ZnF2

Abstract >>
Based on a cluster approach, the local structure of the rhombic Cu2+ center in a ZnF2 crystal is investigated by using the high-order perturbation formulas of electron paramagnetic resonance (EPR) parameters g-factors gi (i = x, y, z) and hyperfine structure constants Ai in rhombically compressed octahedral symmetry. According to the studies, the local axial distortion angle Δα' (≈ 2.9°) in the impurity center is found to be by ~2.5 larger than the host value, which is characterized as a contraction and stretching of the parallel and perpendicular bond lengths by about 0.116 Å and 0.058 Å respectively. This results in a more compressed ligand octahedron because of the Jahn—Teller effect via the interaction of the vibrations of impurity-ligand bonds in the Cu2+ center. The reasonableness of the results is also discussed.



5.
THEORETICAL STUDY ON THE STRUCTURES AND PROPERTIES OF (Br2AlN3)n (n = 1—4) clusters, density functional theory (DFT), structural feature, IR spectra, thermodynamic properties CLUSTERS

Q.Y. Xia, D.X. Ma, D.J. Li, W.W. Zhao
Keywords: (Br2AlN3)n (n = 1—4) clusters, density functional theory (DFT), structural feature, IR spectra, thermodynamic properties clusters, density functional theory (DFT), structural feature, IR spectra, thermodynamic properties

Abstract >>
To look for the single-source precursors, the structures and properties of (Br2AlN3)n (n = 1—4) clusters, density functional theory (DFT), structural feature, IR spectra, thermodynamic properties clusters are studied at the B3LYP/6-311+G* level. The optimized (Br2AlN3)n (n = 24) clusters, density functional theory (DFT), structural feature, IR spectra, thermodynamic properties clusters all possess cyclic structures containing AlNαAl linkages. The relationships between the geometrical parameters and the oligomerization degree n are discussed. The gas-phase structures of the trimers prefer to exist in the boat-twisting conformation. As for the tetramer, the most stable isomers have the S4 symmetry structure. The IR spectra are obtained and assigned by the vibrational analysis. The thermodynamic properties are linearly related with the oligomerization degree n as well as with the temperature. Meanwhile, the thermodynamic analysis of the gas-phase reaction suggests that the oligomerization be exothermic and favorable under high temperature.



6.
STRUCTURAL, ELECTRONIC, AND VIBRATIONAL PROPERTIES OF ACETYLENE ON Pd(100) DOPED WITH Sn OR Pb: A DFT CLUSTER MODEL STUDY

P. Matczak
Keywords: acetylene adsorption, PdSn catalyst, PdPb catalyst, DFT

Abstract >>
Some structural, electronic, and vibrational properties of the acetylene (C2H2) molecule adsorbed at various sites on the Pd(100) surface doped with Sn or Pb are determined theoretically. The calculations were performed using the B3LYP hybrid density functional, and the Sn- or Pb-doped Pd(100) surfaces were represented by a cluster model approach. It is found that the geometry of the C2H2 molecule adsorbed in di-σ configurations is highly perturbed with respect to the structure of acetylene in the gas phase. By contrast, the geometry of acetylene adsorbed in π configurations on the doped surfaces shows a much smaller distortion. Apart from calculating the properties of the adsorbed C2H2 molecule, the effect of the dopants, i.e. Sn and Pb atoms, on these properties is established by comparing the properties of acetylene adsorbed on the Sn- or Pb-doped Pd(100) surfaces with its properties on the monometallic Pd(100) surface. The results indicate that the geometry of the adsorbed C2H2 molecule is similar on the doped and monometallic Pd(100) surfaces.



7.
CARBOMETALLIC DERIVATIVES OF C1v AND C5v BORANES: ENUMERATION AND IDENTIFICATION OF SUBSTITUTION ISOMERS AND THE CALCULATION SCHEME OF THE PROPERTIES OF C5v BASED ON PASCAL'S TRIANGLE NUMBERS

V. M. Smolyakov, D. V. Sokolov, D. Yu. Nilov, V. V. Grebeshkov
Keywords: cycle index, generating functions, chiral and achiral substitution isomers, additive schemes, boranes, pair and multiple non-valence interactions, molecular graph, polygonal numbers, Pascal's triangle

Abstract >>
Combinatorial analysis methods are employed to solve the problem of determining the number and form of X-substituted (X, XY, … are some substituents) of carbometallic derivatives of boranes (C5H5)Co(2B9H11) C1v and (C5H5)Co(5B6H11) C5v (over vertices) based on Polya's theorem. formulas of Z symmetry and generating functions of the number of chiral and achiral substitution stereoisomers are determined. Family distributions of the isomers depending on the form and number of substituents and depending on the number m of possible substitution sites are found. Mono-, di-, and tri-X-substituted (X = CH3, F, ) isomers of (55)(C5B6H11) C5v are identified. Based on the partition of simple (n) and triangular numbers (K3) of Pascal's triangle, additive schemes are obtained which take into account valence and non-valence pair interactions of atoms in the polyhedron framework and contain 2, 6, and 23 parameters for the calculation of properties of -substituted borane (C5H5)Co(5B6H11) C5v.



8.
REASONS FOR THE LINE BROADENING IN THE EPR SPECTRA OF COPPER IONS IN Li2–2xZn2+x(MoO4)3 lithium-zinc molybdate crystals

A. A. Ryadun, V. A. Nadolinny, A. A. Pavlyuk, S. F. Solodovnikov, E. G. Boguslavskii
Keywords: EPR of transition metal ions, double molybdate crystals, scintillators

Abstract >>
An EPR study of Li2–2xZn2+x(MoO4)3 crystals activated by copper ions shows that they occupy the 2 site, one of the three possible sites of both lithium and zinc. In the EPR spectra of Cu2+ copper a broadening of HFS lines and a nonequidistant splitting between them, which are unusual for the orientation ͠|| gzz,Azz, are observed. In this work possible reasons for such a broadening of HFS lines from copper ions are analyzed: a distortion of the oxygen octahedron due to the introduction of copper ions, second order perturbation theory corrections, superposition of HFS from 63Cu and 65Cu isotopes, and the effect of the charge redistribution in the oxygen octahedron because the cation vacancy providing charge compensation can be located at different distances from the copper ion. It is shown that the first three reasons do not explain the features observed in the EPR spectra. In the case of cation vacancies located in the 3 site and remote at different distances from the copper ion, the charge redistribution in the oxygen octahedron of copper should occur along with the dispersion of HFS parameters and the g-factor. The studies performed in X and Q bands confirm this assumption. The width of HFS lines from copper ions in the EPR spectra measured in the Q band is three times more compared to that measured in the band.



9.
PARALLEL AND DISTRIBUTED COMPUTING IN PROBLEMS OF SUPERCOMPUTER SIMULATION OF MOLECULAR LIQUIDS BY THE MONTE CARLO METHOD

A. V. Teplukhin
Keywords: liquid, water, supercomputer, simulation, Monte Carlo, algorithm, parallel computing, MPI

Abstract >>
An effective strategy of molecular Monte Carlo simulation is proposed. The strategy is based on a combination of two key approaches to parallel computing. The advantage of spatial (domain) decomposition is the high scalability of computing algorithms by splitting "big tasks" into several simultaneously solvable subtasks. However, the domain size in this method can be reduced to a certain limit only. Particle decomposition (division of program loops into portions) is, by contrast, very efficient in the study of small and medium size objects, but is poorly scalable and quickly exhausts the computer system memory with increasing size of the model. The combination of the approaches helps "neutralize" their limitations and create efficient supercomputing programs for the study of molecular models consisting of hundreds of millions of atoms.



10.
QUANTITATIVE ESTIMATION OF THE DISCONTINUOUS FUNCTION OF THE SOLVENT IN AQUEOUS ELECTROLYTE SOLUTIONS

V. N. Afanasev
Keywords: adiabatic compressibility, hydration of salts, hydration numbers, discontinuous function of the solvent

Abstract >>
The adiabatic compression method is used to determine quantitative solvation parameters such as hydration numbers h, the molar adiabatic compressibility of hydrated complexes βhVh, the volume V1h and compressibility β1h of water in ion hydration shells, and several other properties in the temperature range 278.15-323.15 K. Hydration numbers are used to determine the verified activity coefficient of the solvent, γR. The concentration dependence of the coefficient is shown to be a discontinuous function, with the discontinuity point corresponding to the complete solvation boundary.



11.
HYDRATION OFα-ALANINE IN AQUEOUS SODIUM CHLORIDE AND UREA SOLUTIONS

V. P. Korolev, A. L. Serebryakova
Keywords: sodium chloride, urea, alanine, aqueous solutions, partial volumes, hydration numbers

Abstract >>
The hydration number of α-alanine in aqueous urea solutions is greater than in aqueous NaCl solutions; the ratio of the hydration numbers increases from 0.2 (m = 1) to ≈2 (m = 6). Given the same partial volumes of water, the hydration numbers of α-alanine in the two systems are close to each thr.



12.
PSEUDOSYMMETRY IN CRYSTALLINE COMPOUNDS WITH HIGHLY SYMMETRIC SUBLATTICES

A. S. Poplavnoi
Keywords: pseudosymmetry, electron density, Bravais sublattices, elementary excitation spectra

Abstract >>
The features of pseudosymmetry in crystalline compounds with highly symmetric sublattices are discussed. The symmetry of sublattices higher than the crystal symmetry is manifested in elementary excitation spectra in the form of degenerations and quasidegenerations. The topology of spectral branches is not related to the value of the parameter estimating the degree of pseudosymmetry on the basis of the electron density fraction, which is invariant with respect to operations corresponding to additional symmetry.



13.
CRYSTAL STRUCTURE OF SODIUM-STRONTIUM PARATUNGSTATE B, Na6Sr2[W12O40(OH)2]∙24H2O

S. V. Radio, N. I. Gumerova, V. N. Baumer
Keywords: paratungstate B anion, isopolytungstate, crystal structure, FTIR spectroscopy, single crystal X-ray analysis

Abstract >>
From the acidified solution of the Na2WO4–HNO3Sr(NO3)2H2O system, the white crystals of sodium-strontium paratungstate B Na6Sr2[W12O40(OH)2]∙24H2O (I) 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 I is solved: monoclinic, space group P21/n, a = 12.5435(3) Å, b = 12.1544(3) Å, c = 18.8080(4) Å, β = 93.440(2)°, V = 2862.28(12) Å3 at T = 293 K, Z = 2, ρcalc = 4.207 g/cm3. Found that [W12O40(OH)2]10 paratungstate B anions are cross-linked in a layer via the SrO9 and NaO6 polyhedra, and cross-linking in a three-dimensional structure occurs via the NaO6 and NaO7 polyhedra. By DTA, the thermal properties of the salt are studied. By FTIR spectroscopy, it is found that under annealing of I the [W12O40(OH)2]10 paratungstate B anion exists in the structure up to 200 C.



14.
STRUCTURE OF MN(II), CO(II), NI(II), AND CU(II) COMPLEXES WITH TRIFORMYLMETHANE

E. V. Tretyakov, S. E. Tolstikov, G. V. Romanenko, A. S. Bogomyakov, R. Z. Sagdeev, V. M. Novotortsev, V. I. Ovcharenko
Keywords: manganese(II) complexes, cobalt(II) complexes, nickel(II) complexes, copper(II) complexes, 1,3-dicarbonyl compounds, X‑ray diffraction analysis

Abstract >>
Previously unknown [ML2(H2O)n] bischelates, where M is Mn(II), Co(II), Ni(II), or Cu(II) and L is deprotonated triformylmethane, are studied by X‑ray diffraction analysis. It is revealed that in the crystals of all compounds there are multiple hydrogen bonds linking bischelate molecules into polymer layers or a single framework. The character of the temperature dependence of the effective magnetic moment [ML2(H2O)n] indicates the existences of weak intracrystalline exchange interactions between the unpaired electrons of the paramagnetic centers.



15.
CRYSTAL STRUCTURE OF A NEW SUPRAMOLECULAR Ni(II)N6-BENZYLAMINOPURINE COMPOUND

M. Xia, C.-L. Wei
Keywords: Ni(II) N6-benzylaminopurine compound, crystal structure, supramolecule

Abstract >>
A new mononuclear Ni(II) N6-benzylaminopurine supramolecule [Ni(6-BA-H2)2(H2O)4]⋅(R)2⋅4H2O (1) (6-BA = N6-benzylaminopurine (C5H2N3NH)(NH)CH2(C6H5), H3R = 5-sulfosalicylic acid (C6H3)CO2H(OH)SO3H) is firstly synthesized by the volatile method. Compound 1 possesses a 3D supramolecular structure built via H-bonds and π—π stacking interactions. In the structure, a mononuclear [Ni(6-BA-H2)2(H2O)4]6+ cation, in which the Ni(II) ion is 6-coordinated, bears six positive charges, and a fully deprotonated R3− anion is located in the void surrounding the mononuclear cation to balance the charge.



16.
CHARACTERIZATION AND CRYSTAL STRUCTURE STUDY OF A NEW Cu(II) COMPLEX OF PYRIDINE-2,6-DICARBOXYLIC ACID AND ANILINE CONTAINING A WATER CLUSTER

U. Ibotomba Singh, R.K. Bhubon Singh, M.J. Borah, J.P. Jasinski, J.A. Golen
Keywords: pyridine-2,6-dicarboxylate complex, monoclinic, octahedral, copper(II) complex, water cluster, crystal structure

Abstract >>
A new monoclinic Cu(II) salt complex (C6H6N)2+ [Cu(2,6-dipico)2]2–⋅6H2O, (2,6-dipico = pyridine-2,6-dicarboxylic acid) is synthesized and characterised by CHN analyses, IR, UV-Vis, magnetic susceptibility measurements, and single crystal X-ray crystallography. The structure contains two pyridine-2,6-dicarboxylate species as tridentate ligands with protonated aniline acting as a counter cation and six uncoordinated water molecules. The complex crystallizes in the monoclinic space group C2/c with unit cell parameters a = 20.9393(4) Å, b = 7.94330(10) Å, c = 19.9093(4) Å, V3) = 2932.32(9), Z = 4. Crystal packing is stabilized by N—H…O, OHO intermolecular hydrogen bonds and weak ππ interactions. The water molecules are trapped by a cooperative association of coordination interactions forming water clusters as well as by a hydrogen bond to the Cu (II) complex.



17.
A STUDY OF THE STRUCTURE AND PROPERTIES OF MIXED-LIGAND Cu(II) COMPLEXES WITH HEXAFLUOROACETYLACETONE AND METHYL-, PHENYL-KETOIMINES

P. A. Stabnikov, I. V. Korolkov, V. V. Krisyuk, I. A. Baidina
Keywords: mixed-ligand copper(II) complexes, crystal structure, molecular packing, volatility

Abstract >>
The synthesis and X‑ray single crystal study of two mixed-ligand Cu(II) complexes are performed: (CH3C(NCH3)CHC(O)CH3)(CF3C(O)CHC(O)CF3)Cu (1) (space group P21/c , a = 7.0848(12) Å, b = 17.854(3) Å, c = 11.837(2) Å, β = 100.495(6)°, V = 1472.4(4) Å3, Z = 4), (CH3C(NC6H5)CHC(O)CH3)⋅(CF3C(O)CHC(O)CF3)Cu (2) (space group P-1, a = 9.1119(4) Å, b = 9.6954(4) Å, c = 11.1447(6) Å, α = 113.784(2), β = 92.383(2), γ = 95.402(2), V = 893.52(7) Å3, Z = 2). The structures are molecular, formed from neutral mixed-ligand copper complexes. The central copper atom has the (3O+N) coordination environment with average Cu–O distances of 1.948 Å and CuN of 1.932 Å; the chelate OCuN angle (average) is 94.0. In the structures, the complexes are linked into dimeric associates with Cu…Cu distances of 3.197 Å (for 1) and 3.246 Å (for 2). The volatility of mixed-ligand complexes 1 and 2 is in between of that of the starting homo-ligand complexes.



18.
CRYSTAL STRUCTURES OF ALLYLTRIPHENYL-PHOSPHONIUM HALOGENOCUPRATES(I)

G. V. Noshchenko, N. F. Salivon, B. Zarychta, V. V. Olijnyk
Keywords: crystal structure, copper(I), allyl phosphonium, stacking, weak hydrogen bonds, phenyl embrace, homoconjugation, hyperconjugation

Abstract >>
Alternating-current electrochemical synthesis is used to obtain for the first time halogenocuprates of an allyl derivative of phosphonium of the composition (CH2=CHCH2(C6H5)3P)CuX2 (X = Br (I), Cl (II)). Compound I crystallizes in the space group P21, a = 9.6341(3) Å, b = 12.4167(4) Å, c = 9.9618(4) Å, β = 117.484(5)°, Z = 2. Compound II crystallizes in the space group 21/n , a = 9.9725(5) Å, b = 15.4586(8) Å, c = 13.7557(5) Å, β = 90.429(4), Z = 4. In the structures of I and II quasilinear CuX2anions are held by іH⋯ hydrogen bonds inside a framework formed by the stacking of phenyl groups from H2=HCH2(65)3P+ cations. Allyl groups are not involved in coordination with copper (I) atoms.



19.
STRUCTURAL FEATURES OF THIOCARBAMIDE DERIVATIVES OF SOME LANTHANIDE IODIDES

T. A. Antonenko, L. Yu. Alikberova, D. V. Albov, N. S. Rukk
Keywords: lanthanide iodides, thiocarbamide, aquacomplexes, structure, synthesis

Abstract >>
Data on the synthesis, IR spectroscopy, and single crystal XRD are presented for thiocarbamide compounds of the composition [Ln(H2O)9]I3⋅2CS(NH2)2, where Ln = Dy (I) and Yb (II). The structural features of [Ln(H2O)9]I3⋅2CS(NH2)2 (Ln = Pr, Nd, Eu, Gd, Dy, Ho, Er, and Yb) are discussed. The compounds of thiocarbamide with Pr, Nd, Eu, Gd, and Dy iodides are found to form the first isostructural series characterized by a continuous network structure, while with Ho, Er, and Yb iodides the second isostructural series with a layered type structure is formed.



20.
A NEW POLYMORPH OF METHIMAZOLE: SINGLE CRYSTAL AND POWDER X-RAY DIFFRACTION STUDY

O. A. Lodochnikova, A. V. Bodrov, A. F. Saifina, L. E. Nikitina, I. A. Litvinov
Keywords: methimazole, polymorphism, hydrogen bonds

Abstract >>
A new polymorph of 1-methyl-4-imidazoline-2-thione has been first discovered and studied by X-ray diffraction. The crystal of the new polymorph is monoclinic, the asymmetric part of the cell contains three independent molecules. In the crystal, the key compound is in the form of planar hydrogen-bonded dimers due to the interactions of the N–H…S type. The new modification is of an intensely yellow color in contrast to the previously known colorless forms, is characterized by a lower density but stronger hydrogen bonds; it is formed as a minor impurity to main triclinic polymorph.



21.
CRYSTAL STRUCTURES AND ANTIBACTERIAL ACTIVITY OF HYDRAZONE DERIVATIVES FROM 1H-INDOL-3-ACETOHYDRAZIDE

F. Zhi, N. Shao, Q. Wang, Y. Zhang, R. Wang, Y. Yang
Keywords: hydrazone derivative, synthesis, X-ray diffraction, antibacterial activity

Abstract >>
A series of three new hydrazone derivatives C22H19N3O2 (1), C17H13ClN4O3 (2), and C21H24N4O2⋅CH4O (3) obtained by the condensation of 1H-indol-3-acetohydrazide with 2-methoxynaphthaldehyde, 2-chloro-5-nitrobenzaldehyde, and 4-diethylaminosalicylaldehyde, respectively, in methanol, ia prepared. The compounds are characterized by elemental analysis, IR spectra, 1H NMR spectra, and single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic space group P21/n with unit cell dimensions a = 17.740(2) Å, b = 5.621(1) Å, c = 18.573(3)Å, β = 92.659(2)°, V = 1850.0(6)Å3, Z = 4, R1 = 0.0610 and wR2 = 0.1155. Compound 2 crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 29.178(2)Å, b = 8.195(1)Å, c = 14.372(1)Å,Å= 109.446(2), V = 3240.5(5)Å3, Z = 8, R1= 0.0452 and wR2 = 0.1028. Compound 3 crystallizes in the monoclinic space group Pc with unit cell dimensions a = 6.579(1)Å, b = 15.112(2)Å, c = 10.676(2)Å,Å= 90.030(2), V = 1061.4(3)Å3, Z = 2, R1 = 0.0535 and wR2 = 0.1123. The single crystal X-ray structural determination reveals that the molecules of the compounds are much twisted due to the lack of efficient conjugation. Preliminary biological tests indicate that the compounds are effective antibacterial material.



22.
TARTARIC ACID AND ITS O-ACYL DERIVATIVES. 7. CRYSTAL STRUCTURE OF O-p-ANISOYL-D-TARTARIC ACID AND ITS DIMETHYLAMMONIUM SALT TRIHYDRATE

G. Wesela-Bauman, T. Boinski, P. Dominiak, H. Hajmowicz, L. Synoradzki, M. Wierzbicki, B. Woliński, K. Woźniak, K. Zawada
Keywords: tartaric acids, acyl derivatives, anisoyl

Abstract >>
Monoacylated derivatives O-p-anisoyl-D-tartaric acid and its N,N-dimethylammonium salt are synthesized by the partial hydrolysis of O,O'-di-p-anisoyl-D-tartaric acid. Crystal and molecular structures of both compounds have been determined and analyzed. In both of them, some strong and moderate strength [O—H…O] hydrogen bonds exist between the carboxylic units. The intermolecular hydrogen bonds link the adjacent fragments forming infinite one-dimensional chains parallel to the X-axis.



23.
A QUANTUM CHEMICAL STUDY OF SILSESQUIOXANES: H8Si8O12, Me8Si8O12, H@Me8Si8O12, He@Me8Si8O12+, AND He@Me8Si8O12

S. G. Semenov, M. E. Bedrina
Keywords: silsesquioxanes, endocomplexes, helium, cubic symmetry, structure, polarizability, PBE0, B3LYP, cc-pVTZ, MP2

Abstract >>
Quantum chemical PBE0 and B3LYP/cc-pVTZ, PBE0, B3LYP, RHF and MP2/6-31G(d,p) methods are employed to calculate the structural parameters of octa(silsesquioxane) H8Si8O12 and octa(methylsilsesquioxane) Me8Si8O12. These molecules and complexes @Me8Si8O12, @Me8Si8O, and @Me8Si8O12 have highly symmetric (Oh) equilibrium configurations. With the use of the PBE0 method and a cc-pVTZ multicenter basis set common for the complex and its components coincidence is achieved between the calculated polarizability of a free He atom and the experimental value of 0.21 Å3 and the polarizability depression of 0.17 Å3 was found for e@Me8Si8O12. In order to avoid the false conclusion about molecular symmetry the calculations of the structure of silsesquioxanes must be performed with sufficiently high accuracy (Int = ultrafine and Opt = tight in the use of the GAUSSIAN program).



24.
STRUCTURE OF THE COMPLEX OF HEXANUCLEAR MANGANESE PIVALATE WITH ISONICOTINAMIDE

E. Yu. Fursova, V. I. Ovcharenko, A. S. Bogomyakov, G. V. Romanenko
Keywords: Mn(II, III) complexes, polynuclear compounds, ditopic ligands, isonicotinamide, coordination polymers, X-ray crystallographic analysis

Abstract >>
The structure of the [Mn6(O)2(Piv)10L2] compound, where Piv is the pivalate anion and L is isonicotinamide, is investigated. Its solid phase is found to be formed by polymeric layers within which hexanuclear fragments {Mn6(O)2(Piv)10} are bound by bidentate bridging L. The molecules of the solvent (Me2CO or EtOAc) in which the synthesis was performed are incorporated into the inter-layer space of the crystal.



25.
CRYSTAL STRUCTURAL AND THERMAL PROPERTIES OF A 1D CADMIUM COORDINATION POLYMER [Cd(PhCOO)2(bbbm)]n

C.-H. He, C.-H. Jiao, G.-H. Cui
Keywords: bis(benzimidazole), hydrothermal, cadmium(II), 1D coordination polymer

Abstract >>
A new 1D cadmium coordination polymer [Cd(PhCOO)2(bbbm)]n (1) (bbbm = 1,1'-(1,4-butanediyl)bis-1H-benzimidazole ) is synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TG, and X-ray single-crystal diffraction. Compound 1 crystallizes in the triclinic system, space group P-1 with a = 10.4289(17) Å, b = 12.5198(9) Å, c = 12.6130(9) Å, α = 118.4260(10)°, β = 95.1990(10), γ = 94.3820(10), V = 1428.8(3) Å3, Z = 2. In the structure of 1, each cadmium center is six-coordinated in a strongly distorted octahedron by two N and four O atoms; an infinite one-dimensional linear chain was built by the flexible bbbm ligand that adopts a bis-monodentate bridging mode linking CdII atoms.



26.
IN SITU SYNTHESIS AND STRUCTURE OF FeCl4(4,4'-DIETHYL-4,4'-BIPYH) (BIPY = BIPYRIDINE)

W.-T. Chen, Z.-G. Luo, D.-S. Liu, Y.-P. Xu, Q.-Y. Luo
Keywords: bipyridine, hydrothermal reaction, in situ, viologen

Abstract >>
A novel viologen(4,4'-bipyridinium)-based compound FeCl4(4,4'-diethyl-4,4'-bipyH) (1) (bipy = bipyridine), in which 4,4'-diethyl-4,4'-bipyH (MQ+) was generated in situ, is synthesized via the hydrothermal reaction and structurally characterized by single crystal X-ray diffraction. The crystal structure analysis reveals that the title compound features an isolated structure based on 4,4'-diethyl-4,4'-bipyH moieties and an iron atom terminally bound by four chlorine atoms. The 4,4'-diethyl-4,4'-bipyH moieties and (FeCl4) anions are interconnected by hydrogen bonds to form a 3D supramolecular framework.



27.
CRYSTAL STRUCTURE OF DIACETATO-BIS(2-METHYL-2-PROPYLAMINE)ZINC(II)

E. Kandasamy
Keywords: zinc acetate, amine, hydrogen bond, NH---O interaction

Abstract >>
The diacetato-bis(2-methyl-2-propylamine)zinc(II) compound crystallizes in the triclinic system, space group P-1 with unit cell parameters a = 10.0144(10) Å, b = 10.2687(10) Å, c = 10.5149(10) Å, α = 115.184(2)°, β = 97.489(2), γ = 114.066(2), ν = 830.85(14) Å3. The obtained solid state structure of (tBuNH2)2Zn(OOCCH3)2 shows both inter- and intramolecular NH---O hydrogen bond interactions which are analyzed.



28.
CRYSTAL AND MOLECULAR STRUCTURE OF N-METHYL-Bis(2-HYDROXYETHYL)AMMONIUM (4-CHLORPHENYLSULFONYL)ACETATE

M. G. Voronkov, V. S. Fundamenskii, S. N. Adamovich, . A. Zelbst, A. A. Kashaev, V. A. Brouskov, R. G. Mirskov, A. N. Mirskova
Keywords: (4-chlorphenylsulfonyl)acetic acid, N-methyl-bis(2-hydroxyethyl)amine, ionic liquid, molecular structure, single crystal X‑ray diffraction study

Abstract >>
By X‑ray diffraction the crystal and molecular structure of N-methyl-bis(2-hydroxyethyl)ammonium (4-chlorphenylsulfonyl)acetate 4-ClC6H4SO2CH2COO⋅CH3N+H(CH2CH2OH)2 synthesized by the interaction of (4-chlorphenylsulfonyl)acetic acid with N-methyl-bis(2-hydroxyethyl)amine is studied.



29.
STRUCTURE OF ETHYL 3-(4-TOLYL)HYDRAZONO-2,4-DIOXOPENTANOATES

T. V. Levenets, V. O. Kozminykh, A. O. Tolstikova
Keywords: one-pot three-component condensation, ethyl 3-(4-tolyl)hydrazono-2,4-dioxopentanoates, single crystal XRD

Abstract >>
As a result of one-pot three-component condensation of acetone with diethyl oxalate and p -tolyl diazonium chloride of ethyl 3-(4-tolyl)hydrazono-2,4-dioxopentanoates p-tolyl diazonium diethyloxalate and chloride, ethyl ether of 3-(4-tolyl)hydrazono-2,4-dioxopentanoic acid is obtained. The structure of the synthesized compound is studied.



30.
ABSOLUTE CONFIGURATION OF 3-ACETYLBETULINIC ACID

E. M. Suleimen, K. Van Hecke, L. Van Meervelt, Deborggraeve Wim, Dehaen Wim
Keywords: betulinic acid, 3-acetoxybetulinic acid, single crystal X-ray diffraction analysis

Abstract >>
The absolute configuration of 3-acetoxybetulinic acid is determined by single crystal X-ray diffraction.



31.
UNUSUAL CRYSTAL AND MOLECULAR STRUCTURE OF TRIS(2-HYDROXYETHYL)AMMONIUM FLUORIDE

M. G. Voronkov, A. A. Korlyukov, T. A. Kochina, . A. Zelbst
Keywords: tris(2-hydroxyethyl)ammonium halides, protatranes, molecular structure, single crystal X‑ray diffraction study

Abstract >>
According to the X‑ray diffraction data, the crystal and molecular structure of tris(2-hydroxyethyl) ammonium fluoride (FN+H(CH2CH2OH)3, fluoroprotatrane, substantially differs from other halo protatranes XN+H(CH2CH2OH)3 (X = Cl, Br, and I). At X = F, to the endo-molecular LP of the nitrogen atom the HF molecule having the minimum ionic radius in a series of X anions is bonded. The geometry of fluoroprotatrane and the cation packing in the crystal are analyzed.