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Journal of Structural Chemistry

2014 year, number 3

1.
SEMI-CANONICAL MO IN THE VARIED OPEN SHELL METHOD AND RELATED APPROACHES

A. V. Luzanov
Institute for Single Crystals, National Academy of Sciences of Ukrainian, Kharkov
Keywords: restricted Hartree-Fock method, Roothaan theory, canonical MOs, Koopmans theorem, Aufbau principle

Abstract >>
The self-consistency schemes previously developed in J. Struct. Chem ., 30, N 5, p. 3 (1986) are shown to belong to the class of semi-canonical orbital schemes. In the derivation they explicitly involve only a part of canonical Koopmans orbitals in the iteration process. In particular, within the restricted Hartree-Fock method for a non-degenerate case a semi-canonical variational scheme based on the matrix elements of the unrestricted Hartree-Fock method is studied. Errors present in the above mentioned work in the description of the scheme of a varied open shell are corrected. A possible generalization for the case of Roothaan type degeneration is proposed and specific examples of low-spin and high-spin states with a violated Aufbau filling principle are considered.
																								



2.
POINT CHARGES AND ATOMIC MULTIPOLE MOMENTS OF Si AND O IN AMORPHOUS SiO 2 FOR THE ESTIMATION OF THE ELECTROSTATIC FIELD AND POTENTIAL

A. V. Larin1,2
1Moscow State University, Department of Chemistry, Russia, Moscow, Russia
2Plasmonics Ltd., Ural Build., Skolkovo Center, Moscow oblast, Moscow, Russia
Keywords: amorphous oxide, atomic multipole moment, electrostatic potential

Abstract >>
In order to estimate atomic multipole moments (s) and charges in the model of amorphous SiO2 a hybrid B3LYP functional with 30% of the Hartree-Fock Hamiltonian in the exchange part with the 88-31G*(Si)/8-411G*(O) basis set and the CRYSTAL06 package are used. A 192-atomic unit cell of amorphous SiO2 is chosen as a model, the calculations with which agree well with the experimental static factor of neutron scattering. The second optimized model of amorphous SiO2 (a-SiO2) with a smaller number of defects is prepared with the use of the VASP package and full optimization of the initial a-SiO2 model. For both models the atomic charges and s are calculated (up to the fourth order included) and their approximation is performed. The approximation quality is compared for these models and with a model for crystalline systems whose s were previously calculated. The conclusions are drawn about the applicability of charge and estimates within the approaches such as the embedded cluster.
																								



3.
NEW POLYMORPHIC TYPES OF DIAMOND

E. A. Belenkov, V. A. Greshnyakov
Chelyabinsk State University, Chelyabinsk, Russia
Keywords: simulation, diamond, diamond polymorphs, sublimation energy, bulk modulus, electron density of states, X-ray diffraction pattern

Abstract >>
The results of calculations by PM3 and LDA-DFT methods of the structure and properties of six new polymorphic types of diamond, in which all atomic sites are crystallographically equivalent, are presented. The structures of LA5 (Cmca), LA7 (mcm), and LA8 (I41/ amd ) phases are obtained as a result of stitching graphene layers and of CA9 (Fd3m), CA10 (R3m), and CA11 (P63/mmc) phases by stitching fullerene-like clusters. For these phases the geometrically optimized structures are calculated and the structural parameters, density, sublimation energy, bulk modulus, electron density of states, and X-ray diffraction pattern are measured. It is found that the properties of polymorphic types of diamond depend on the degree of their structure deformation in comparison with the cubic diamond structure.
																								



4.
MOLECULAR STRUCTURE OF BIS(DIPYRROLYLMETHANATES) OF d-METALS ACCORDING TO THE QUANTUM CHEMICAL CALCULATIONS BY THE 6 METHOD

A. A. Ksenofontov1, G. B. Guseva2, E. V. Antina2, A. I. Vyugin2
1Ivanovo State University of Chemistry and Technology, Ivanovo, Russia
2Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: bis(dipyrrolylmethanates), helicates, quantum chemical calculations, 6 method, molecular structure, reactivity

Abstract >>
Quantum chemical calculations of the molecular structure of bis (dipyrrolylmethanates) of cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), and mercury(II) of the composition [2L2] are performed using the PM6 method within the Gaussian 09W program package. The lengths of M-N coordination bonds, the values of dihedral angles formed by N-M-N bonds, the distances lM⋯M between the M⋯M atoms are optimized. It is noted that the regularities obtained from the analysis of the results of quantum chemical calculations of the molecular structure of [2L2] helicates reliably reflect the main trends of changes in their physicochemical properties depending on the nature of a complexing agent and the features of the ligand structure.
																								



5.
CORRELATIONS: ALKYLSILANE PROPERTY - POLYNOMIAL COEFFICIENTS OF THE ADJACENCY MATRIX OF THE MOLECULAR GRAPH

D. Yu. Nilov, V. M. Smolyakov
Tver State University, Tver, Russia
Keywords: molecular graph, adjacency matrix A' of a heterogeneous molecular graph, eigenvalues, characteristic polynomial coefficients, additive scheme, alkylsilanes, enthalpy of formation

Abstract >>
Based on the characteristic polynomial coefficients (CPCs) of the adjacency matrix A' of heterogeneous molecular graphs of the molecules containing a tetravalent heteroatom >Si< (>Ge<, >Sn<), etc. in the chain, a 13-constant additive scheme for the calculation of their physicochemical properties is obtained. The structural meaning of CPCs of the adjacency matrix A' is established. By the formula obtained the formation enthalpies ΔfH0gas, 298 K of SiCnH2n+2 alkylsilanes not studied experimentally are calculated.
																								



6.
VIBRATIONAL SPECTRA AND ELECTRONIC STRUCTURE OF 1-GERMATRANOL, 1,1-QUASI-GERMATRANDIOLE, AND 1,1,1-HYPOGERMATRANTRIOLE (HO)4-nGe(OCH 2CH2)nNR3-n (R = H, Me; n = 1-3)

I. S. Ignatev1, M. G. Voronkov2,3, T. A. Kochina2, G. S. Samokhin2, V. V. Belyaeva3, S. Ya. Khaikin4
1St. Petersburg State University, St. Petersburg, Russia
2Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, St. Petersburg, Russia
3Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
4Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, St. Petersburg, Russia
Keywords: 1-germatranol, 1,1-quasi-germatrandiole, 1,1,1-hypogermatrantriole, molecular structure, vibrational spectra

Abstract >>
IR spectra of 1-germatranol, 1,1-quasi-germatrandiole, 1,1,1-hypogermatrantriole with a general formula (HO)4-nGe(OCH2CH2)n NR3-n ( n = 1-3) are obtained. At the B3LYP/ aug-cc-pVDZ density functional level the equilibrium structures and vibrational spectra of these compounds along with their hydrogen-bonded dimers are calculated. Based on the calculations the band assignment is performed in the IR spectra of 1-germatranol, 1,1-quasi-germatrandiole, and 1,1,1-hypogermatrantriole. The existence of dimers is manifested in the IR spectra as the absence of bands in the frequency ranges characteristic of the bending vibrations of Ge-OH groups and the presence of bands in the vibrational range of hydrogen-bonded germatranyl groups.
																								



7.
VIBRATIONAL SPECTROSCOPIC INVESTIGATION OF METHYL(5-[2-THIENYLCARBONYL]-1H-BENZIMIDAZOL-2-YL: A COMPARATIVE DENSITY FUNCTIONAL STUDY

O. Alver1, C. Parlak2, Kaya M. Fatih2, G. Dikmen1, L. Genc,1
1Anadolu University, Eskişehir, Turkey
2Dumlupı nar University, Kütahya, Turkey
Keywords: nocodazole, vibrational spectra, TED, DFT, SQM

Abstract >>
FT-IR and Raman spectra of methyl(5-[2-thienylcarbonyl]-1H-benzimidazol-2-yl (nocodazole) are experimentally examined in the region of 4000-400 cm–1. The optimized geometric parameters, conformational equilibria, normal mode frequencies, and corresponding vibrational assignments of nocodazole (C14H11N3O3S) calculated by means of the B3LYP hybrid density functional theory (DFT) method using the 6-31++G(d,p) basis set. Vibrational assignments are made based on the total energy distribution (TED) and the thermodynamic functions, highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of nocodazole are calculated. Calculations are employed for four energetically possible conformers of nocodazole (N1, N2, N3 and N4) in the gas phase. A comparison between the experimental and theoretical results indicates that the B3LYP method is able to provide satisfactory results for predicting vibrational wavenumbers if calculated values are scaled properly and the structural parameters.
																								



8.
SOLID-STATE STRUCTURES OF 2-(4-HYDROXYPHENYL)-SUBSTITUTED PHENALENE-1,3-DIONE AND INDAN-1,3-DIONE

M. Marinov1, N. Stoyanov2, A. Ugrinov3, S. Angelova4, I. Wawer5, M. Pisklak5, V. Enchev4
1Agricultural University, Plovdiv, Bulgaria
2University of Ruse, Bulgaria
3North Dakota State University, Fargo, North Dakota, United States
4Institute of Organic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria
5Medical University of Warsaw, Warsaw, Poland
Keywords: 2-(4-hydroxyphenyl)-phenalene-1,3-dione, 2-(4-hydroxyphenyl)-indan-1,3-dione, solid-state NMR, X-ray, quantum chemical calculations

Abstract >>
The structure of 2-(4-hydroxyphenyl)-substituted indan-1,3-dione and phenalene-1,3-dione is investigated using a combination of solid-state NMR, single crystal X-ray analyses and quantum chemical calculations. It is shown that 2-(4-hydroxyphenyl)-1,3-indandione exists as a diketo tautomer while 2-(4-hydroxyphenyl)-1,3-phenalenedione exists in the enol form.
																								



9.
A STUDY OF THE CHEMICAL BOND TYPES IN FILMS DEPOSITED FROM BIS(TRIMETHYLSILYL)ETHYLAMINE BY PECVD

E. N. Ermakova1, V. G. Kesler2, Yu. M. Rumyantsev1, M. L. Kosinova1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Rzhanov Institute of Semiconductor Physics, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: silicon carbonitride, thin films, PE CVD, X-ray photoelectron spectroscopy, IR spectroscopy

Abstract >>
Silicon carbonitride films are synthesized by plasma enhanced chemical vapor deposition from bis(trimethylsilyl)ethylamine and helium or ammonium mixtures. The structure of chemical bonds in the films is studied by X-ray photoelectron and IR spectroscopy. The data on the main types of bonds present in silicon carbonitride films deposited under different synthesis conditions are obtained. It is shown that the use of ammonia at a low deposition temperature provides the synthesis of films with a simultaneous formation of Si-C, Si-N, and C-N bonds. The main bonds in films obtained from a bis(trimethylsilyl)ethylamine and helium mixture are Si-C and Si-N. The chemical structure of films obtained at high synthesis temperatures is close to SiCx regardless of the type of the additional gas used.
																								



10.
BULK PROPERTIES AND HYDRATION NUMBERS OF AMMONIUM NITRATE AND AMMONIUM CHLORIDE IN SOLUTION: A STRUCTURAL AND THERMODYNAMIC ANALYSIS

V. P. Korolev
Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: apparent and partial volumes, hydration numbers, ammonium chloride, ammonium nitrate

Abstract >>
The apparent volumes of the salts in the systems H2O - NH4Cl (298 K) and H2O - NH4NO3 (273, 298, and 323 K) are reproduced with an accuracy of 0.03-0.01 cm 3/mol by the equation φ = φ0 + Aw20,5 + w2, where w2 is the salt content (mass fractions). The study shows that there is a correspondence between the critical (for determining the hydration number) structural parameters-the intrinsic volume of the electrolyte and the volume of water in ion hydration shells-and the limiting (at w2 = 1) partial molar volumes of the components. The hydration numbers at infinite dilution are 6.9 for NH4Cl at 298 K and 9.1, 6.7, and 6.4 for NH4NO3 at 273, 298, and 323 K. The water volume in ion hydration shells decreases in the sequence: NO3¯ Cl-, and NH4+ The hydration numbers decrease with increasing salt concentration. The study shows that within a simpler model φ = φ0 + aw20,5, the hydration numbers are temperature independent.
																								



11.
COHERENCE ASSEMBLY PHENOMENON IN THE TYPICAL STRUCTURES OF HETEROPOLYNIOBATES

S. V. Borisov, S. A. Magarill, N. V. Pervukhina
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: crystallographic analysis, coherence assembly, cation framework, building blocks, polyoxoniobates, menezesite, aspedamite

Abstract >>
Crystallographic analysis has provided evidence for single cation frameworks formed from preordered cation positions in the individual building blocks (modules) constituting the basis of structures. We propose to call this phenomenon coherence assembly . According to the mechanical wave concept of the crystalline state, coherence assembly dictates the rules of mutual packing of “rigid” structural fragments. This study investigates the typical structures of heteropolyniobates: Na12[Ti2O2][SiNb12O40]×4H2O (I), menezesite Ba2MgZr4[BaNb12O42]×12H2O (II), and the menezesite-isostructural aspedamite □12(Fe3+,Fe 2+)3Nb4×[Th(Nb,Fe3+)12O42]×(H2O,OH)12 (III).
																								



12.
CRYSTAL STRUCTURE OF A TRINUCLEAR COMPLEX OF ZINC(II) WITH 2,6-DI-TERT-BUTYL- p-QUINONE 1'-PHTHALAZINYLHYDRAZONE

A. E. Goldberg1, M. A. Kiskin1, L. D. Popov2, S. I. Levchenkov3, I. N. Shcherbakov2, Yu. P. Tupolova2, V.A. Kogan2
1Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
2Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
3Chemistry Department, Southern Federal University, Rostov-on-Don, Russia
Keywords: hydrazones, tautomerism, 1-hydrazine phtalazine, zinc(II) complex, X-ray crystallography, density functional theory

Abstract >>
2,6-Di-tert -butyl-p -quinone 1'-phthalazynylhydrazone (HL) is synthesized; the total energies and geometry of the possible hydrazone tautomeric forms are calculated by quantum chemical methods. The hydrazone phthalazone tautomer is shown to be the most stable, which is well consistent with the 1H NMR spectroscopic data for hydrazone. An X-ray crystallographic analysis is performed of the hydrazone-based Zn(II) trinuclear complex, in which zinc atoms are linked by the diazine bridge of the phthalazine cycle and two pivalate bridges. The geometric properties of the monodeprotonated hydrazone residue in the complex are similar to the calculated data for the phthalazone hydrazone tautomeric form.
																								



13.
CRYSTAL STRUCTURE OF POLYNUCLEAR PIVALATE NI(II) COMPLEXES WITH BUTANEDIOL

G. V. Romanenko, O. V. Kuznetsova, E. Yu. Fursova
Institute of the International Tomography Center, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: nickel(II), polynuclear compounds, pivalates, butanediol, single crystal X-ray diffraction study

Abstract >>
Using single crystal X-ray diffraction the structure of polynuclear [Ni6(OH)4(Piv)7(HOC 4H8O)(HPiv)4], {K4[Ni12(CO3)2(Piv)16(OH)8(HOC4H8OH)2]}HPiv, {[Ni6(OH)4(Piv)6(HOC4H8O)(Me2CO)(HOC4H8OH)2]4(Piv)4}, and {K[Ni2L2(Piv)3]} complexes, where HOC4H8OH is 1,4-butanediol, HPiv is pivalic acid, and L is the anion of nitroxyl radical 2,2,5,5-tetramethyl-4-(3',3',3'-trifluoro-2'-oxy-1'-propenyl)-3-imidazolin-1-oxyl is determined.
																								



14.
CRYSTAL AND MOLECULAR STRUCTURES OF BIS(2,2,6,6-TETRAMETHYL-3-METHYLAMINOHEPTAN-5-ONATE) COPPER(II) AND NICKEL(II)

P. A. Stabnikov1, S. I. Dorovskikh1, N. V. Pervukhina1, L. G. Bulusheva1, G. B. Romanenko2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Institute of the International Tomography Center, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: copper(II) and nickel(II) chelates, crystal structure, steric effects

Abstract >>
Two bis-chelates M(tmih)2 (M = Cu(II), Ni(II), tmih = (CH3)3C(NCH3)CHCOC(CH3)3)- are synthesized and their crystal structures are determined using XRD (Bruker APEX-II diffractometer with a CCD detector, lMo Ka, lCu Ka, graphite monochromator, T = 240(2) K and 296(2) K): Cu(tmih)2 (I) (space group P21/c , a = 12.9670(8) Å, b = 18.4921(9) Å, c = 11.0422(6) Å,β= 93.408(4)°, V = 2643.1(3) Å3, Z = 4) and Ni(tmih)2 (II) (space group P21/c , a = 12.810(2) Å, b = 18.529(2) Å, c = 11.243(2) Å, β = 91.959(7), V = 2667.1(6) Å3, Z = 4). The complexes are isostructural; the coordination polyhedron of metal atoms is a flattened tetrahedron formed from two O atoms (Cu-O of 1.901(2) Å, 1.892(2) Å, Ni-O of 1.845(2) Å, 1.833(2) Å) and two N atoms (Cu-N of 1.976(3) Å, 1.972(3) Å, Ni-N of 1.911(2) Å, 1.920(2) Å) of the ligand; the chelate OMN angles (M = Cu(II), Ni(II)) are in the 87.4-93.1 range; the OMO and NMN angles are 162.2 and 167.2 in I, 171.1 and 173.2 in II. The complexes have the molecular structures formed from isolated molecules bonded by van der Waals interactions. Using a quantum chemical hybrid M06 method, the structures of copper(II) chelates with the H, CH3, CH2CH3, CH(CH3)2, and C(CH3)3 substituents at the nitrogen atom are calculated. Found that with a bulky substituent at the nitrogen atom, the formation of chelates is hindered due to the intraligand repulsion between the atoms of this substituent and the tert-butyl group.
																								



15.
COORDINATIVE PROPERTIES OF THE PYRIDINE-2-CARBALDEHYDE THIOSEMICARBAZONE LIGAND TOWARDS NI(II)

C. Graiff, S. Canossa, G. Predieri
Università di Parma, Italy
Keywords: nickel, thiosemicarbazone complexes, crystal structure

Abstract >>
Three crystal structures of Ni compounds containing bis(pyridine-2-carbaldehyde thiosemicarbazone) ligand (HL), namely (pyridine-2-carbaldehyde thiosemicarbazonato)(pyridine-2-carbaldeyde thiosemicarbazone) nickel(II) nitrate hydrate [Ni(HL)L][NO 3]×(H 2O) (1), bis(pyridine-2-carbaldehyde thiosemicarbazone) nickel(II) dinitrate [Ni(HL) 2][NO 3] 2 (2a), and bis(pyridine-2-carbaldehyde thiosemicarbazone) nickel(II) dinitrate dihydrate [Ni(HL) 2][NO 3] 2×2(H 2O) (2b) are determined by X-ray diffraction methods. Comparative structural studies are carried out.
																								



16.
CRYSTAL STRUCTURES OF [Pd(NH3)3(NO2)][Rh(NH3)2(NO2)4] AND [PdEn2][Rh(NH3)(NO2)5]·0.75H2O

S. P. Khranenko1, N. V. Kuratieva1,2, S. A. Gromilov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State University, Novosibirsk, Russia
Keywords: palladium, rhodium, ethylenediamine, nitrite, double complex salt, single crystal X-ray diffraction study, crystal chemistry

Abstract >>
The structure of double complex salts [Pd(NH3)3(NO2)][Rh(NH3)2(NO2)4] and [PdEn2][Rh(NH3)(NO2)5]×0.75H2O is determined by single crystal X-ray diffraction. In the structures, the main structural moieties are identified.
																								



17.
STRUCTURAL STUDY OF COMPLEX [Rh(NH3)5(NO2)](NO3)2·H2O, [Rh(NH3)5(NO2)][Pd(NO2)4], AND K2[Rh(NH3)(NO2)5]H2O SALTS

I. A. Baidina, A. I. Smolentsev, A. V. Belyaev
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: complexes, double complex salts, rhodium, palladium, single crystal X-ray diffraction study, 14N NMR, nitro ammines

Abstract >>
Compounds [Rh(NH 3) 5(NO 2)](NO 3) 2×H 2O (I) with a = 7.6230(3) Å, b = 7.6230(3) Å, c = 10.3584(4) Å, space group I -42 m , Z = 2, d calc = 2.026 g/cm 3, V = 601.93(4) Å 3, Rh-NH 3 eq = 2.074 Å, Rh-NH 3 ax (NO 2) = 2.048 Å; [Rh(NH 3) 5(NO 2)][Pd(NO 2) 4] (II) with a = 8.095(3) Å, b = 22.422(8) Å, c = 7.887(3) Å, b = 98.559(17)°, space group Cc , Z = 4, d calc = 2.461 g/cm 3, V = 1415.6(9) Å 3, Rh-NH 3 eq = 2.069 Å, Rh-NH 3 ax = 2.090 Å, Rh-NO 2 = 2.002 Å; K 2[Rh(NH 3)(NO 2) 5]×H 2O (III) with a = 7.5177(5) Å, b = 20.9856(15) Å, c = 7.7017(5) Å, space group Cmc 2 1, Z = 4, d calc = 2.439 g/cm 3, V = 1215.05(14) Å 3, Rh-NH 3 ax (NO 2) = 2.094 Å, Rh-NO 2 eq = 2.030 Å are synthesized and studied using single crystal X-ray diffraction.
																								



18.
STRUCTURE, SYNTHESIS, AND THERMAL PROPERTIES OF trans-[Ru(NO)(NH3)4(SO4)]NO3·H2O

S. A. Adonin1, P. A. Abramov1, S. I. Uskov2
1Novosibirsk State University, 630090 Pr. Lavrentieva 3
2Novosibirsk State University, 630090 st. Pirogova, 2
Keywords: ruthenium, nitroso complexes, amino complexes, sulfato complexes, synthesis, single crystal X-ray diffraction analysis, thermal analysis

Abstract >>
In treatment of trans-[Ru(NO)(NH3)4(OH)]Cl2 with concentrated sulfuric acid on heating trans -[Ru(NO)(NH3)4(SO4)](HSO 4)×H2O (I) is obtained with a yield close to quantitative. In the interaction of the saturated solution of I with a saturated NaNO 3 solution a trans-[Ru(NO)(NH3)4(SO4)]NO3×H2O (II) precipitate forms whose structure is determined by single crystal XRD: space group 2 12 12 1, a = 6.8406(3) Å, b = 12.6581(5) Å, c = 13.3291(5) Å. A monodentately coordinated sulfate ion is in the trans -position to the nitroso group. Compound II is characterized by IR spectroscopy, powder XRD, and diffuse reflectance spectroscopy. The process of its thermolysis is studied; by differential scanning calorimetry the thermal effect of the dehydration reaction occurring on heating to 120°C (D H = 58.9 ± 1.5 kJ/mol) is estimated. The final product of the thermolysis of II is a mixture of Ru and RuO2.
																								



19.
CRYSTAL STRUCTURES OF 2-FERROCENYLMETHYLIDENEHYDRAZONO-1,3-DITHIANE AND 2-FERROCENYLMETHYLIDENEHYDRAZONO-1,3-DITHIEPANE

Wu Ping
Universities of Shandong, Shandong, P. R. China
Keywords: X-ray diffraction, dithiane, dithiepane, ferrocenyl

Abstract >>
Two compounds of 2-ferrocenylmethylidenehydrazono-1,3-dithiane (1) and 2-ferrocenylmethylidenehydrazono-1,3-dithiepane (2) are synthesized and their single crystal structures are determined by the X-ray diffraction method. Compound 1 belongs to the orthorhombic Pca 2 1 space group with the cell parameters: a = 13.989(4) Å, b = 5.785(2) Å, c = 18.231(5) Å, V = 1475.4(7) Å 3; while compound 2 crystallizes in a monoclinic symmetry, P 2 1/ c space group with a = 15.320(2) Å, b = 5.8028(6) Å, c = 36.584(4) Å, b = 91.932(1) and V = 3250.4(6) Å 3.
																								



20.
N-H⋯S HYDROGEN BONDING MOTIFS IN CRYSTALLINE SOLIDS OF 1,2,4-TRIAZOLE-5-THIONES: APPLICATION OF THE CAMBRIDGE STRUCTURAL DATABASE. R 2 2 (8) RING MOTIF

Irena Wawrzycka-Gorczyca
Maria Curie-Sklodowska University, Lublin, Poland
Keywords: N-H⋯S hydrogen bond, R (8) ring motif, 1,2,4-triazole-5-thiones, dimer, Hirshfeld surface, fingerprint plot, CSD, Cambridge Structural Database

Abstract >>
A database study on the N-H⋯S hydrogen bonding ring motif ( R 2 2(8)) for 1,2,4-triazole-5-thiones is reported. The R 2 2(8) ring is one of the most general ring motifs observed in the crystallographic literature, however, up to now the ring synthon built by the N-H⋯S interaction has not been particularly described. Probably, in multi-heteroatom systems, other structure-determining stronger interactions may take precedence over weaker N-H⋯S interactions. On the other hand, in recent years, considerable importance has been given to structures determined through N-H⋯S interactions. It is also common in the crystals of 1,2,4-triazole-5-thione derivatives.
																								



21.
A NOVEL PROCESS FOR MAKING ALKALINE IRON OXIDE NANOPARTICLES BY A SOLVO THERMAL APPROACH

D. Mishra, R. Arora, S. Lahiri, S.S. Amritphale, N. Chandra
Council of Scientific and Industrial Research, Advanced Materials and Processes Research Institute, Bhopal, India
Keywords: alkaline iron oxide, nanoparticles, solvo thermal

Abstract >>
In the present work alkaline iron oxide nanoparticles are synthesized by a novel solvo thermal approach and characterized exhaustively by various complementary techniques. Field emission scanning electron microscopy (FESEM) studies reveal that the size of nanoparticles is in the range of 31.5 nm to 96.9 nm. Energy-dispersive X-ray spectroscopy spectral analysis reveals the presence of oxygen, carbon, iron, and sodium. The X-ray diffraction studies confirm the formation of tetragonal NaFeO 2 as the major phase along with orthorhombic NaFeO 2×H 2O and rhombohedral FeCO 3 (siderite) as the minor phases. Fourier transform infrared spectroscopy exhibits peaks due to the stretching and bending vibrations of O-H, C=O, CH 3-N, CH 3, C-H, C-N, and Fe-O groups. Differential scanning calorimetry (DSC) results display an endothermic peak at 100.85 C and a very small endothermic peak at 791.56 C with 819.73 mJ and 349.28 mJ energies respectively. These DSC peaks can be correlated with thermal gravimetric analysis (TGA) peaks representing 31.04 % weight loss and 7.70 % weight loss respectively in the sample at around 160 C and 980 C respectively.
																								



22.
THEORETICAL STUDY OF THE ELECTRONIC CONDUCTION THROUGH ORGANIC NANOWIRES

Z. Chamani1, Z. Bayat1, S.J. Mahdizadeh2
1Islamic Azad University, Quchan, Iran
2Ferdowsi University of Mashhad, Mashhad, Iran
Keywords: cis- and trans-butadiene, molecular wire, HOMO-LUMO gap, electric field, gold cluster

Abstract >>
A substantial amount of researches have been carried out on the electron transport properties of gold surfaces. In order to study the role of linkage in the conductive properties of a molecular wire, different linkers such as sulfur, nitrogen, oxygen, CS, SH, NS, and CN are considered in our study. It is found that nitrogen or sulfur linkages can bond Au covalently to cis - and trans -butadiene, whereas on the other hand, oxygen linkage with the same shows a weak interaction and a non-covalent character. Further, this research is also an attempt to study the dependence of the molecular electronic structure of gold-molecule complexes on the external electric field. In addition, electronic conduction has been investigated from the perspective of alteration in shape of molecular orbitals and the development of the HOMO-LUMO gap of molecule-gold complexes under the effect of an electric field.
																								



23.
CRYSTAL STRUCTURE OF CYCLIC SULFINAND SULFONAMIDES OF THE THIAZINE SERIES: CONFORMATION, INTRAAND INTERMOLECULAR INTERACTIONS

E. V. Mironova1, O. A. Lodochnikova1, D. B. Krivolapov1, Ya. V. Veremeichik2, V. V. Plemenkov2, I. A. Litvinov1
1Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, Kazan, Russia
2Kant Baltic Federal University, Kaliningrad, Russia
Keywords: sulfinamides, sulfonamides, crystal and molecular structure, X-ray crystallographic analysis, hydrogen bonds, DFT-calculations, topological analysis

Abstract >>
An X-ray crystallographic study of a new compound is performed and the structure of five sulfin- and sulfonamides of the thiazine series is discussed. The conformation of the thiazine ring in all structures (a distorted boat ) is stabilized by the intramolecular interaction of the C-H…N type. The nitrogen atom of the thiazine ring has a pyramidal configuration. The geometry of isolated molecules is calculated at density functional theory level (PBE1PBE, 6 -31G(d,p)) and compared to that observed in the crystals. In the crystal structures different packing motifs are implemented with the formation of supramolecular associates of different types due to classical hydrogen bonds such as N-HO.
																								



24.
FEATURES OF THE INTRAMOLECULAR STRUCTURE OF BRANCHED POLYMER SYSTEMS IN SOLUTION

N. V. Kutsevol1, T. N. Bezuglaya1, M. Yu. Bezuglyi1,2
1Shevchenko National University of Kiev, Kiev, Ukraine
2Kaunas University of Technology, Kaunas, Lithuania
Keywords: branched polymers, molecular architecture, dendrimers, star-like copolymers

Abstract >>
The review is devoted to the synthesis and properties of branched polymer structures of a controlled molecular architecture. The work considers the main methods to obtain branched macromolecules. The results of both theoretical calculations and experimental studies of the structure and features of the behavior of the mentioned systems in solution are analyzed and generalized. The promising use of branched polymer systems as an alternative to linear systems is noted.
																								



25.
STRUCTURE OF BIS(2-METHYLIMINO-3-PENTEN-4-ONATO) NICKEL(II). PROPERTIES OF NICKEL(II) KETOIMINATES

P. A. Stabnikov, O. S. Koshcheeva, N. V. Pervukhina, G. I. Zharkova
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: nickel(II) bis-chelate, crystal structure, volatility

Abstract >>
A new volatile complex Ni(mi-aa)2 [mi-aa = CH3C(NCH3)CHC(O)CH3)] is synthesized and its crystal structure is determined (APEX DUO diffractometer with a 4C CCD detector, lMo K a, graphite monochromator, T = 100 K). Crystallographic data for Ni(mi-aa) 2 are as follows: space group Pbca , a = 5.4058(3) Å, b = 11.8684(6) Å, c = 19.8472(10) Å, V = 1273.4(1) Å3, Z = 4. The Ni(II) atom is coordinated by the O and N atoms of two ligands. The Ni-O and Ni-N distances are 1.8390(9) Å and 1.926(1) Å; the chelate ONiN angle is 92.52(4)°. The complex has the molecular structure formed from the isolated molecules of Ni(mi-aa)2 bound by van der Waals interactions. For some complexes, the TG study is performed and the intermolecular interaction energy in the crystals is calculated.
																								



26.
INFINITE 1D WATER CHAINS PRESENT IN COMPLEXES OF Co(II) AND Zn(II) WITH 4,4',6,6'-TETRAMETHYL-2,2'-BIPYRIMIDINE

N. Ma, B. M. Ji
Luoyang Normal University, 471022, P. R. China, Luoyang
Keywords: complex, Co(II), Zn(II), tmbpm, crystal structure, intermolecular hydrogen bond, water chain

Abstract >>
Two new transition metal complexes [Co(tmbpm)Cl2(H2O)]×2H2O (1) and [Zn(tmbpm)Cl2]×2H2O (2) (where tmbpm = 4,4',6,6'-tetramethyl-2,2'-bipyrimidine) are synthesized and characterized by IR and single crystal X-ray diffraction. The tmbpm adopts chelating coordination mode in the two mononuclear complexes. Both 1 and 2 form 2D supramolecular structures containing an infinite 1D water chain through hydrogen bonds.
																								



27.
HYDROTHERMAL SYNTHESIS OF A NANO-ROD MERCURY(II) METAL-LIGAND COORDINATION COMPOUND

Y. Hanifehpour1, A. Khataee2, Sang Woo Joo1, Bong-Ki Min1
1Yeungnam University, Gyongsan, South Korea
2University of Tabriz, Tabriz, Iran
Keywords: HgMercury(II), metal-ligand, nano-rod, hydrothermal

Abstract >>
A novel nano-rod mercury(II) coordination compound [Hg (BINH)I 2] (1), (BINH is the abbreviation of benzylideneisonicotinohydrazide) is synthesized by a hydrothermal method that produces the coordination compound at a nanosize level. The new nanostructure is characterized by scanning electron microscopy, powder X-ray diffraction, elemental analysis, and IR spectroscopy. Compound 1 was structurally characterized by single crystal X-ray diffraction and the single-crystal structure of this complex shows that each mercury(II) center is four-coordinated with two N-donor atoms from tow BINH ligands and tow iodo anions. Self-assembly of this complexes is pereformed by CH⋯I and p-p stacking interactions. The supramolecular features in these complexes are controlled by weak directional intermolecular interactions.
																								



28.
MOLECULAR AND CRYSTAL STRUCTURES OF bis-TETRAZOLATE AMMONIUM SALT AND bis-TETRAZOLE MONOHYDRATE

G.Y.S.K. Swamy, K. Ravikumar
Center for X-ray Crystallography, CSIR-Indian Institute of Chemical Technology, Hyderabad, India
Keywords: crystal structure, bis-tetrazole, X-ray diffraction, hydrogen bonding

Abstract >>
The title compounds bis -tetrazolate ammonium salt (I) and bis -tetrazole monohydrate (II) are synthesized and studied by single crystal and powder X-ray diffraction, IR and elemental analyses. Compound I crystallizes in the monoclinic space group C 2/ m , a = 8.8862(17) Å, b = 11.2334(21) Å, c = 3.7269(7) Å, b = 99.4(6), V = 367.03 Å 3 (12), Z = 2. Compound II crystallizes in the monoclinic space group P 2 1/ c , a = 5.1701(9) Å, b = 4.7506(8) Å, c = 15.2197(24) Å, b = 107.2(7), V = 357.09(10) Å 3, Z = 2. In the structure of I, both ammonium cation and bis -tetrazolate counter-anion are located on twofold crystallographic axes, moreover, the bis -tetrazolate anion has a mirror plane passing through the C1-C1a bond. In the crystal structure of (II), the bis -tetrazole molecule sits on the twofold axis (bisecting the C1-C1a bond), whereas the solvent water molecule occupies a general position. In the crystal structure of (I), the molecules are packed via N-HN intermolecular interactions. In the crystal structure of (II), the molecules are packed via N-HO and O-HO intermolecular interactions. In addition, the crystal packing of both structures is further strengthened by p-p stacking interactions.