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Journal of Structural Chemistry

2013 year, number 5

1.
π-SYSTEM IN A STRONG ELECTRIC FIELD. ANALYSIS OF ELECTRON UNPAIRING

A. V. Luzanov
Institute for Single Crystals, National Academy of Sciences of Ukraine, Ukraine, Kharkiv
Keywords: full configuration interaction, electron unpairing index, biradicality, aromaticity, antiaromaticity

Abstract >>
The action of a strong electric field on conjugated π-systems is studied within the method of full configuration interaction. The behavior of systems in the field is analyzed by means of the electron unpairing measure: the number Neff of effectively unpaired electrons. For Neff formal asymptotic rules are derived, which correspond to extreme values of the external field. Field induced biradicaloid π-states are studied in detail.



2.
GENESIS OF THE PHONON SPECTRA OF 2B452 AND 1362 CRYSTALS WITH A CHALCOPYRITE LATTICE FROM THE VIBRATIONAL STATES OF THEIR SUBLATTICES

A. V. Kopytov, A. S. Poplavnoi, M. K. Ufimtsev
Kemerovo State University, Kemerovo
Keywords: phonon spectrum, lattice dynamics, density of state, sublattices, chalcopyrite

Abstract >>
The phonon spectra of a series of 2452 and 1362 crystals with the chalcopyrite structure are calculated in the Keating model in the basis set of polarization vectors of their sublattices. The dependences of frequency values and partial contributions of sublattices to the polarization vectors on the chemical composition are studied. The effect of the mass ratio and the strengths of covalent bonds between the compound components on the phonon spectrum formation is found.



3.
ADSORPTION BEHAVIOR OF CO AND C2H2 ON THE GRAPHITE BASAL SURFACE: A QUANTUM CHEMISTRY STUDY

T. Hosseinnejad1, F. Nazari2, R.A. Mirzaei2
1Alzahra University, Vanak, Tehran, Iran
2Shahid Rajaee Teacher Training University, Tehran, Iran
Keywords: graphite basal surface, carbon monoxide, acetylene, physical interaction energy, quantum chemical calculations

Abstract >>
The adsorption of CO and C2H2 molecules on the perfect basal surface of graphite is investigated by adopting cluster models in conjunction with quantum chemical calculations. The noncovalent interaction potential energy curves for three different orientations of CO and C2H2 molecules with respect to the inert basal plane of graphite are calculated via semi-empirical and Möller-Plesset ab initio methods. Then, we have considered the effects of interaction energies on the C≡O and C≡C bond lengths by performing the partial geometry optimization procedure on the CO-graphite and C2H2-graphite systems in various intermolecular distances. The computational analysis of all physical noncovalent potential energy curves reveals that the relative configurations in which CO and C2H2 molecules approach the graphite sheet from out of the plane have stronger interaction energy and so is more favorable from the energetic viewpoint. This means that the graphite layer prefers to increase its thickness via the chemical vapor deposition of CO and C2H2 on the graphite.



4.
FORMATION MECHANISM OF 1,3-bis(2-OXOPROPYL)-3-1,2,3-BENZOTRIAZOLIUM TRIIODIDE IN THE ALKYLATION REACTION OF 1,2,3-BENZOTRIAZOLE WITH 1-IODOPROPAN-2-ONE

V. A. Shagun, I. A. Dorofeev, L. G. Shagun
1A. E. Favorsky Irkutsk Institute of Chemistry, Russian Academy of Sciences, Irkutsk
2A. E. Favorsky Irkutsk Institute of Chemistry, Russian Academy of Sciences
Keywords: quantum chemical calculation, ionic liquid, reaction mechanism, alkylation, 1,2,3-benzotriazole, 1-iodopropan-2-one

Abstract >>
Within DFT (B3LYP) methods the potential surface of the interaction between 1-iodopropan-2-one and 1,2,3-benzotriazole resulting in the formation of 1,3-bis(2-oxopropyl)-3-1,2,3-benzotriazolium triiodide is studied. A mechanism consisting of four steps (N-1-alkylation of 1,2,3-benzotriazole, elimination of molecular iodine during partial reduction of 1-iodopropan-2-one with hydrogen iodide, formation of the triiodide structure, and formation of 1,3-bis(2-oxopropyl)-3-1,2,3-benzotriazolium) is proposed. Thermodynamic and kinetic parameters of these steps are obtained.



5.
A STUDY OF THE STRUCTURE AND ENERGY OF β-DIKETONATES. XVIII. MOLECULAR STRUCTURE OF CHROMIUM AND COBALT TRIS-ACETYLACETONATES ACCORDING TO QUANTUM CHEMICAL CALCULATIONS AND GAS ELECTRON DIFFRACTION

N. V. Tverdova1, G. V. Girichev1, S. A. Shlykov1, N. P. Kuzmina2, A. A. Petrova1, I. G. Zaitseva2
1Ivanovo State University of Chemistry and Technology, Ivanovo
2Department of Chemistry Moscow State University, Moscow
Keywords: tris-acetylacetonates, chromium, cobalt, molecular structure, gas electron diffraction, quantum chemistry, mass spectrum

Abstract >>
The molecular structure of chromium and cobalt tris-acetylacetonates is studied by the synchronous electron diffraction and mass spectrometric experiment and quantum chemically. It is found that molecules have the D3 symmetry with internuclear distances rh1(Cr–O) = 1.960(4) Å and rh1(CoO) = 1.893(4) Å. Quantum chemical calculations by the DFT methods with different basis sets yield a structure well consistent with that found in the experiment. Changes in the structural parameters of chromium and cobalt b-diketonate complexes whose ligands differ in CH3, C(CH3)3, CF3 substituents are considered.



6.
FORMATION CONDITIONS OF A MAGNETICALLY ORDERED PHASE ε-Fe2O3: A FMR IN SITU STUDY

S. S. Yakushkin, G. A. Bukhtiyarova, O. N. Martyanov
G. K. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk
Keywords: ferromagnetic resonance, supermagnetic nanoparticles, heterogeneous catalysts, in situ

Abstract >>
The ferromagnetic resonance (FMR) method in situ is used to study the initial stages of the formation of ε iron oxide nanoparticles deposited on silica gel at temperatures up to 600°C. It is shown that at high-temperature treatment of starting samples obtained by impregnation with an iron(II) sulfate solution, supermagnetic ε-Fe2O3/SiO2 nanoparticles form with a narrow size distribution. An analysis of the FMR data in comparison with the data of other methods enables the formulation of the formation conditions for systems of deposited ε-Fe2O3 nanoparticles without other polymorph impurities.



7.
CRYSTAL STRUCTURE OF TWO COMPLEXES CONTAINING TRIS-(β-DIKETONATO)MAGNATE ANION

E. S. Vikulova, D. A. Piryazev, K. V. Zherikova, N. I. Alferova, N. B. Morozova, I. K. Igumenov
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
Keywords: magnesium, β-diketonates, diamines, single crystal X-ray diffraction, thermogravimetry

Abstract >>
Single crystal XRD is used to determine the structures of the complexes (H2TMEDA)[Mg(ptac)3]2 (1, TMEDA = Me2N(CH2)2NMe2, ptac = tBuCOCHCOCF3) and (H2TMEDA)[Mg(hfac)3](hfac) (2, hfac = CF3COCHCOCF3) at a temperature of 150 K. The crystallographic data for complex 1: a = 10.2919(3) Å, b = 10.9492(4) Å, c = 15.4159(6) Å, α = 87.117(1)°, β = 89.686(1), γ = 79,864(1), space group Z = 1, R = 0.0573; for complex 2: a = 12.9446(2) Å, b = 23.0035(4) Å, c = 13.1473(3) Å, α = 90, β = 98.779(1), γ = 90, space group P21/n, Z = 4, R = 0.0605. The structures are ionic; the metal atom coordinates six oxygen atoms of three β-diketonate ligands. The distances Mg–O in complex 1 are in the range 2.036(2)-2.0920(19) Å; the same distances in complex 2 are in the range 2.051(2)-2.076(2) Å. The spatial packing is determined by the system of hydrogen bonds between the (H2TMEDA)2+ cations and [Mg(ptac)3] (1) or hfac (2) anions. A thermogravimetric study of complex 1 is carried out.



8.
STRUCTURAL FEATURES OF THE COMPONENTS OF COPPER-CERIUM-ZIRCONIUM OXIDE CATALYSTS

È. M. Moroz, V. P. Pakharukova, D. A. Zyuzin
G. K. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk
Keywords: structure of nanomaterials, ceria, zirconia, copper oxide, catalyst

Abstract >>
The structure of supports (ceria and zirconia) for supported copper catalysts for the processes of hydrogen obtaining and purification is studied. The formation features of the structure of zirconia annealed at 300-1000C are identified at different levels: the atomic one and the level of the structural arrangement of secondary particles when the formation of agglomerated block structures with large number of grain interfaces occurs. The formation process of copper oxides on different supports is studied.



9.
INTERPRETATION OF X-RAY PHOTOELECTRON SPECTRA OF FREE NITROXYL RADICALS

L. N. Mazalov1, A. D. Fedorenko1, V. I. Ovcharenko2, E. V. Tretyakov2, E. Yu. Fursova2, N. A. Kryuchkova1, A. V. Kalinkin3, E. V. Trushin3
1A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
2International Tomography Center, Siberian Division, Russian Academy of Sciences, Novosibirsk
3G. K. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk
Keywords: free nitroxyl radicals, X-ray photoelectron spectroscopy, effective charges, spin density, charge transfer model

Abstract >>
N1s and O1s X-ray photoelectron spectra of stable nitroxyl radicals (substituted piperidine-1-oxyl, 2-imidazoline-1-oxyl, and 2-imidazoline-3-oxide-1-oxyl) and also diamagnetic derivatives with a {ONCNO} fragment are measured. It is shown that the structure of N1s and O1s X-ray photoelectron spectra of nitroxyls is determined by charge transfer processes between different parts of the molecule to screen the X-ray hole and the spin-spin interaction of unpaired electrons on the HOMO and 1s level.



10.
X-RAY SPECTRAL AND QUANTUM CHEMICAL STUDY OF THE ELECTRONIC STRUCTURE OF THIACALIX[4]ARENES ANS THEIR ACYCLIC ANALOGS

N. A. Kryuchkova1,2, S. A. Lavrukhina1, G. A. Kostin1,2, L. N. Mazalov1,2, V. G. Torgov1, A. V. Kalinkin3, A. B. Drapailo4
1A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
2Novosibirsk State University
3G. K. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk
4Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Ukraine, Kiev
Keywords: thiacalix[4]arenes, X-ray photoelectron spectroscopy, X-ray emission spectroscopy, DFT method

Abstract >>
An X-ray photoelectron and X-ray emission study of the charge state of thiacalix[4]arenes is performed with a comparison with the data of quantum chemical calculations. Relaxation corrections between the Kohn–Sham orbital energies calculated by the DFT method and experimental parameters of the X-ray emission and photoelectron spectra of the studied compounds are estimated. It is shown that the formation of a cyclic aromatic system in thiacalixarenes results in a decrease in the energy of orbitals involving π interactions of the bridging sulfur atoms and aromatic moieties, which determines the features of the X-ray emission spectra of the studied compounds.



11.
HOMOGENEITY REGIONS OF DOUBLE MOLYBDATES IN THE Na2MoO4–MgMoO4 SYSTEM AND STRUCTURES OF TRICLINIC Na1.50Mg2.25(MoO4)3 AND Na1.68Mn2.16(MoO4)3

S. F. Solodovnikov1,2, Z. A. Solodovnikova1, I. A. Gudkova1, E. S. Zolotova1, V. N. Yudin1,2
1A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
2Novosibirsk State University
Keywords: sodium, magnesium, manganese, double molybdates, nonstoichiometry, homogeneity region, crystal structure

Abstract >>
In the samples of the Na2MoO4–MgMoO4 system quenched in the air at above 600°C, by powder X‑ray diffraction two double molybdates of variable composition are detected: monoclinic alluaudite-like Na42xMg1+x(MoO4)3 (0.05 ≤ x ≤ 0.35) and triclinic Na22 yMg2+y(MoO4)3 (0.10 ≤ y ≤ 0.40) isostructural to previously studied Na2Mg5(MoO4)6. Sodium-magnesium molybdate of the Li3Fe(MoO4)3 structure type is not revealed in this system. By spontaneous flux crystallization, the crystals are obtained and the structures of two triclinic double molybdates of the Na2Mg5(MoO4)6 structure type (space group P1, Z = 1) containing magnesium and manganese are determined. The results of the refinement of site occupancies made it possible to determine the composition of the studied crystals: for the compound with magnesium (Na)0.5(Na0.250.75)(Na0.75Mg 0.25)Mg2(MoO4)3 or Na1.50Mg2.25(MoO4)3 (a = 6.9577(1) Å, b = 8.6330(2) Å, c = 10.2571(2) Å, α = 106.933(1), β = 104.864(1), γ = 103.453(1), R = 0.0188); for the compound with manganese (Na)0.5(Na0.320.68)(Na0.82Mn0.18)Mn2(MoO4)3 or Na 1.64Mn2.18(MoO4)3 (a = 7.0778(2) Å, b = 8.8115(2) Å, c = 10.4256(2) Å, α = 106.521(1), β = 105.639(3), γ = 103.233(1), R = 0.0175). The Na2Mg5(MoO4)6 structure is redetermined and it is shown that actually it corresponds to the composition Na1.40Mg2.30(MoO4)3.



12.
CRYSTAL STRUCTURES OF AZIDO OR THIOCYANATO-COORDINATED NICKEL(II) COMPLEXES WITH TRIDENTATE SCHIFF BASES

S.-S. QIAN1, M. ZHANG2, ZHONG-LU YOU2, HAI-LIANG ZHU1
1Shandong University of Technology, ZiBo, P. R. China
2Liaoning Normal University, Dalian, P. R. China
Keywords: Schiff base, nickel complex, azide, thiocyanate, crystal structure

Abstract >>
A new azido-coordinated nickel(II) complex [NiL1(N3)] (1) and a new thiocyanato-coordinated nickel(II) complex [NiL2(NCS)] (2), where L1 and L2 are the monoanionic forms of Schiff bases 2-[(2-isopropylaminoethylimino)methyl]-6-methylphenol and 2-[(2-dimethlaminoethylimino)methyl]-6-methylphenol respectively, are prepared and structurally characterized by elemental analysis, IR spectra, and single crystal X-ray crystallography. Complex 1 crystallizes in the triclinic space group P-1 with unit cell dimensions a = 8.812(2) Å, b = 9.433(3) Å, c = 9.488(2) Å, α = 81.933(2)°, β = 69.925(2), γ = 84.591(2), V = 732.5(3) Å3, Z = 2, R1 = 0.0291, and wR2 = 0.0734. Complex 2 crystallizes in the monoclinic space group P21/n with unit cell dimensions a = 7.4497(4) Å, b = 6.1933(3) Å, c = 31.5126(18) Å, β = 92.484(2), V = 1452.57(13) Å3, Z = 4, R1 = 0.0307, and wR2 = 0.0668. The Ni atom in each of the complexes is coordinated by three donor atoms of the Schiff base ligand and by one N atom of the azide or thiocyanate ligand, forming a square planar geometry. The azide and thiocyanate anions readily coordinate to the complexes as secondary ligands.



13.
[Ru(NH3)6](MoO4)Cl×3H2O AND [M(NH3)6](ReO4)3×2H2O (M = Ru, Ir). SYNTHESIS AND CRYSTAL STRUCTURE

S. P. Kpranenko1, E. A. Bykova1, K. V. Yusenko1,2, A. P. Tyutyunnik3, S. A. Gromilov1,4
1A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
2Solid-chem GmbH, Bochum, Germany
3Institute of Solid State Chemistry, Ural Division, Russian Academy of Sciences, Ekaterinburg
4Novosibirsk State University
Keywords: ruthenium, molybdenum, rhenium, iridium, complex salt, crystal chemistry, X-ray crystallographic analysis

Abstract >>
X-ray crystallographic analysis is used to determine the crystal structures of [Ru(NH3)6](MoO4)Cl×3H2O and [(NH3)6](ReO4)3×2H2O (M = Ru, Ir) complex salts. The features of the fragment packing are studied.



14.
CRYSTAL STRUCTURE OF SALTS OF THE trans-[Rh(NH3)2(NO2)4] ANION WITH K+, Cs+, Ag+, AND (CH3)4N+ CATIONS

A. V. Belyaev, A. I. Smolentsev, I. A. Baidina, S. V. Tkachev
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk
Keywords: rhodium, trans-diamminetetranitrites, salts, crystal structure, 14,15N NMR

Abstract >>
Complex rhodium(III) salts with the composition trans-[Rh(NH3)2(NO2)4], where = K+, Cs+, Ag+, and N(CH3)4+, are prepared and characterized. The molecular and crystal structures are determined by X-ray crystallography.



15.
STUDY OF THE MOLECULAR AND CRYSTAL STRUCTURE OF A NEW COORDINATION POLYMER OF COPPER(II) NITRATE WITH 4,4,10,10-TETRAMETHYL1,3,7,9-TETRAAZOSPIRO[5.5]UNDECANE-2,8-DIONE

E. E. Netreba
V. I. Vernadsky Taurida National University, Simferopol, Ukraine
Keywords: copper(II), trigonal bipyramid, spirocarbone, coordination polymer, structure, single-crystal XRD

Abstract >>
A coordination polymer {[Cu(C11H20N4O2)2(H2O)]2+×2(NO3)}n (I) is synthesized and analyzed using single-crystal XRD. The crystals are monoclinic: space group P2/c, a = 12.5237(6) Å, b = 7.3310(3) Å, c = 16.8926(8) Å, β = 92.569(4)°, V = 1549.38(13) Å3, rcalc = 1.47 g/cm3, and Z = 2. The copper atom is in a special position in the second-order axis. The coordination polyhedron of the metal is a trigonal bipyramid. In the axial direction, it is coordinated by two oxygen atoms O(1) of the organic ligand molecules connected by the symmetry operation [x, y, 0.5z]; the angle O(1)Cu(1)O(1)i is 175.16(15). In the equatorial direction, the copper atom is coordinated by oxygen atoms O(2) of two ligand molecules connected with the reference molecule by the symmetry operations [x, y, 0.5z] and [x, 1y, 0.5+z] and the water molecule (6) in a special position on the twofold axis. The OCuO angles between the equatorial oxygen atoms are 96.80(16)-131.60(8), and those between the axial and equatorial atoms are 87.58(8)-91.60(10). It is noteworthy that the length of the CuO(1) bond (1.955(2) Å) with the axial carbonyl oxygen atom is somewhat shorter than the bond (2.060(3) Å) with the equatorial atom. Nitrate anions are outside the coordination sphere of the metal. The Cu…Cu distance in the polymer is 8.33 Å. To confirm the purity of the sample of I, the powder X-ray pattern is refined by the Rietveld method; the lattice parameters at room temperature are: a = 12.535(4) Å, b = 7.3161(13) Å, c = 16.841(5) Å, β = 92.11(2), and V = 1543.4(7) Å3.



16.
TAUTOMERISM OF SUBSTITUTED SALICYLALDEHYDE AND 2-DIPHENYLPHOSPHINEBENZALDEHYDE 1'-PHTHALAZINYLHYDRAZONES: X-RAY CRYSTALLOGRAPHY AND QUANTUM CHEMICAL MODELING

S. I. Levchenkov1, L. D. Popov2, I. N. Shcherbakov2, G. G. Aleksandrov3, A. A. Zubenko4, V. A. Kogan2
1Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don
2Chemistry Department, Southern Federal University, Rostov-on-Don
3N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow
4North-Caucasian Zonal Research Veterinary Institute, Novocherkassk, Russia
Keywords: hydrazones, tautomerism, X-ray crystallography, hydrogen bond, density functional theory

Abstract >>
1'-Phthalazinylhydrazones of salicylaldehyde, its substituted derivatives, and 2-diphenylphosphinebenzaldehyde are synthesized and studied. A description is given of the structures salicylaldehyde 1'-phthalazinylhydrazone (1) and 2-diphenylphosphinebenzaldehyde 1'-phthalazinylhydrazone (2), which exist in the crystal in the hydrazonophthalazone tautomeric form. Molecules of hydrazone 1 form in the crystal infinite stacks of hydrogen bonded dimers with intermolecular π-stacking interactions. A quantum chemical calculation is made of the geometry and total energy of the possible tautomers in vacuum and in aqueous and chloroform solutions. The hydrazonophthalazone tautomers are shown to be the most stable in all cases. The X-ray crystallography results are compared with the calculated data.



17.
ADAMANT-1,3,5-TRIYL SUPER DODECAHEDRANES

S. G. Semenov1, Yu. F. Sigolaev2, A. V. Belyakov2
1Saint-Petersburg State University, Saint-Petersburg
2Saint-Petersburg State Institute of Technology, Saint-Petersburg
Keywords: nanostructures, polycyclic compounds, cavitands, icosahedral symmetry, M06-2X/6-31G(d,p), M06-2X/6-311G(d)

Abstract >>
By quantum chemical DFT M06-2X/6-31G(d,p) method, the equilibrium parameters of rigid and stable hydrocarbon clusters of icosahedral symmetry with a dodecahedron structure whose sites are occupied by 20 adamant-1,3,5-triyl moieties linked with each other either directly or through bridges containing two or four carbon atoms are determined. The radius of the smallest studied quasispherical molecules is 1.05 nm and that of the largest one is 1.76 nm. The radius of the inner cavity in them varies from 0.37 nm (C200H260) to 1.06 nm (C320H260). Perfluorination increases the outer and decreases the inner radius of super dodecahedrane.



18.
X-RAY CRYSTALLOGRAPHIC ANALYSIS OF TL2S: AN EXAMPLE OF LAYERED ISOMORPHISM

S. V. Borisov, S. A. Magarill, N. V. Pervukhina
A. V. Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences, Novosibirsk
Keywords: pseudo translational atomic sublattices, variation of the pbs structure type, layered isomorphism of cationic and anionic layers

Abstract >>
In the structure of Tl2S, the pseudo translational sublattice of Tl and S atoms with a rhombohedral primitive subcell aP = 3.09 Å, αP = 81.87° is determined. As opposed to the common PbS structure type, in which single (close-packed) layers of cations and anions alternate, in the structure of Tl2S, there is an alternation of double cationic layers with single anionic layer, while the general geometry of atomic positions (skeleton) of the PbS structure type is retained. Therewith, the atoms of a part of cationic layers occupy the atomic sites of the anionic layers and vice versa.



19.
CRYSTAL STRUCTURE OF CATENA-DI(2-THIOBARBITURATO-O,S)AQUALEAD(II)

N. N. Golovnev1, M. S. Molokeev2
1Siberian Federal University, Krasnoyarsk
2L. V. Kirensky Institute of Physics, Siberian Division, Russian Academy of Sciences, Krasnoyarsk
Keywords: catena-di(μ2-2-thiobarbiturato-O,S)aqualead(II), crystal structure, hydrogen bonds, ππ interaction

Abstract >>
The crystal structure of catena-di(μ2-2-thiobarbiturato-O,S)aqualead(II) C8H8N4O5S2Pb (C4H4N2O2S is 2-thiobarbituric acid, H2TBA) is determined. Crystallographic data for catena-[Pb(H2O)(μ2-HTBA-O,S)2] are as follows: a = 6.5972(1) Å, b = 9.8917(2) Å, c = 10.0893(2) Å, α = 106.702(1)°, β = 93.395(2), γ = 107.48(1), V = 593.82(2) Å3, space group P1, Z = 2. The Pb2+ ion is linked with six monodentate HTBA ligands through two O atoms and four S atoms and also connected with a water molecule. Additionally, there is a shortened Pb–S contact (3.622 Å), given which the complex polyhedron represents a distorted square antiprism. Hydrogen bonds NH⋯O and OH⋯O form a branched three-dimensional network. The structure is also stabilized by theππ-interaction of heterocyclic HTBA ions.



20.
CRYSTAL STRUCTURE OF A NEW TRANSITION METAL-ORGANIC Zn(II) COMPLEX

E.-J. Gao, T.-L. Liu, W. Jiao, L.-L. Jiang, D. Zhang, Y.-J. Zhang, J. Xu, G.-L. Wu
Shenyang University of Chemical Technology, Shenyang 110142, P. R. China
Keywords: Zn(II) complex, 2-mercaptonicotinic acid, crystal structure, coordination

Abstract >>
A novel Zn(II) coordination polymer [Zn2(phen)2]L4×3H2O(1) is synthesized by the reaction of Zn(NO3)2, Phen(1,10-phenanthroline), and L(2-mercaptonicotinic acid) at room temperature and structurally characterized by X-ray single crystal diffraction along with IR spectra and elemental analysis. Title complex 1 belongs to the triclinic system with the space group ( P-1), a = 10.9373(11) Å, b = 11.6201(12) Å, c = 13.1371(14) Å; α = 116.100(1)°, β = 97.717(2), γ = 108.652(2), V = 1344.4(2) Å3; Z = 2, ρcalcd = 1.596 g×cm–3, F(000) = 664, R1 = 0.0708 and wR2 = 0.1823 independent reflections for 18523 observed ones (I > 2σ(I)), and the zinc atom is rendered five-coordinated in a distorted tetragonal pyramid coordination geometry by two nitrogen atoms from the phen molecule, two oxygen atoms from two L molecules, and an oxygen atom from the H2O molecule. Complex 1 forms a 1D chain by O—H⋯O hydrogen bonds from free-water, while the 2D layer structure is formed by CH⋯O hydrogen bonds through the L ligand of adjacent chains. These compounds further result in a 3D network structure by the intermolecular π⋯π stacking interaction of the neighbouring layers.



21.
CRYSTAL STRUCTURE OF A NOVEL COMPLEX [Co(3,3'-bpbc)(H2O)3]×H2O

E.-J. Gao, L.-L. Jiang, D. Zhang, W. Jiao, T.-L. Liu, Y.-J. Zhang, G.-L. Wu, J. Xu
Shenyang University of Chemical Technology, Shenyang 110142, P. R. China
Keywords: 2,2'-bipyridine-3,3'-dicarboxylic acid (3,3'-bpbc), cobalt(II) complex, crystal structure, coordination

Abstract >>
A novel coordination polymer constructed with [Co(3,3'-bpbc)(H2O)3]×H2O(I) (3,3'-bpbc = 2,2'-bipyridine-3,3'-dicarboxylic acid) is successfully synthesized at room temperature and characterized by elemental analysis and IR spectra. The crystal structure of the complex is determined by single crystal X-ray diffraction. The unit cell parameters for complex I are: a = 9.9606(11) Å, b = 9.2552(10) Å, c = 16.0258(17) Å, β = 96.731(0)°, V = 1467.2(3) Å3, Z = 4, space group P2(1)/n. In the crystal, the cobalt(II) ion adopts a hexa-coordinate environment, and the structure units aggregate together to give birth to infinite 1D chains. The 2D and 3D framework is constructed via intermolecular hydrogen bonds.



22.
CRYSTAL STRUCTURE OF 6-FERROCENYL-3-PHENYL-[1,2,4]TRIAZOLO[3,4-b][1,3,4]THIADIAZOLE

Ping Wu
Universities of Shandong, Shandong, P. R. China
Keywords: X-ray diffraction, monoclinic symmetry, triazole, thiadiazole, ferrocenyl

Abstract >>
A new compound of 6-ferrocenyl-3-phenyl-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole is synthesized and its single crystal structure is determined by X-ray diffraction method. The compound belongs to the monoclinic P21/c space group with cell parameters: a = 10.5523(12) Å, b = 13.8414(16) Å, c = 11.4303(13) Å, V = 1603.5(3) Å3.



23.
CRYSTAL STRUCTURE OF TETRA(m-ACETATO)-bis{[1-ETHYL-3-(PYRIDIne-2-YL)CARBAMIDE]COPPER}

Yu. M. Chumakov1, T. B. Capatina2, P. Petrenko1, V. I. Tsapkov2, A. P. Gulea2
1Institute of Applied Physics, Academy of Sciences of Moldova, Moldova, Chisinau
2Moldova State University, Moldova, Chisinau
Keywords: 3d metal complexes, single crystal X‑ray diffraction study, carbamide derivatives

Abstract >>
The crystal structure of tetra(m-acetato)-bis{[1-ethyl-3-(pyridine-2-yl)carbamide]copper} Cu2(L)2(CH3COO)4 (I), where L is 1-ethyl-3-(pyridine-2-yl)carbamide, is determined. The asymmetric unit cell of the crystal structure of I contains a copper complex with two acetate ions and a monodentate molecule of 1-ethyl-3-(pyridine-2-yl)carbamide, which is coordinated via the pyridine nitrogen atom. Due to the symmetry center, binuclear complexes form in the crystal, in which the acetate ions act as bridges between the metal atoms. In them, the coordination polyhedron of the central copper atoms represents an almost ideal tetragonal pyramid. Its base is formed from the oxygen atoms of acetate ions. In the crystal of the binuclear complex, hydrogen bonds form between the acetate ions and the L ligand along with an intramolecular hydrogen bond, which stabilize the conformation of the organic L molecule. Between the neighboring complexes in the crystal, the van der Waals interaction occurs.



24.
STRUCTURAL CHARACTERIZATION OF DICYANIDOBIS( N, N'-DIMETHYLTHIOUREA-κ S)CADMIUM(II)

A. Moghimi1, H.R. Khavasi2, F. Dashtestani1, D. Kordestani3, E. Behboodi1, B. Maddah4
1Islamic Azad University, Tehran North Branch, Tehran, Iran
2Shahid Beheshti University, G. C, Tehran, Iran
3Razi University, Kermanshah, Iran
4Imam Hossein University, Tehran, Iran
Keywords: crystal chemistry, single crystal X-ray diffraction, proton transfer, hydrogen bonding, caffeine, dipicolinic acid

Abstract >>
A reaction between caffeine (caff) and dipicolinic acid = 2,6-pyridine dicarboxylic acid (pydc.H 2) in water results in the formation of a cocrystal compound (pydc.H2.H2O)(caff) 1. The characterization of the resulting crystallohydrate is performed using 1H, 13C NMR and IR spectroscopy and X-ray crystallography. X-ray crystal structure analysis reveals the presence of both starting materials and water in the lattice. It also indicates intensive intermolecular H-bonding interactions between carboxylic acid, caffeine, and water as well as π—π stacking between the pydc.H2 and caff rings as constituents of the cocrystal. The hydrogen bonding and non-covalent interactions play roles in the formation of the cocrystal. The crystal system is triclinic with the space group P- 1 and two formula units per unit cell. The unit cell parameters are a = 6.906(2) Å, b = 8.451(3) Å, c = 14.68 (4) Å with α = 81.51(3°), β = 78.47(3), and γ = 78.14(3). The final R value is 0.0660 for 7943 measured reflections.