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Journal of Structural Chemistry

2015 year, number 1

1.
STRUCTURE AND MAGNETIC PROPERTIES OF IRON-SILICON CLUSTERS IN A MULTICONFIGURATIONAL CALCULATION

K. V. Simon, A. V. Tulub
St. Petersburg State University, St. Petersburg, Russia
Keywords: железокремниевые кластеры, многоконфигурационные неэмпирические расчеты, магнитные моменты, основные и электронно-возбужденные состояния, расчеты DFT, стабильность магнитных свойств при изменении температуры, магма, iron-silicon clusters, multiconfigurational non-empirical calculations, magnetic moments, ground and electronic excited states, DFT calculations, stability of magnetic properties with temperature, magma

Abstract >>
The structure and spin moments of iron-silicon clusters FeSi n are calculated by a multiconfigurational self-consistent field (MCSCF) method in order to refine the spin moments in the ground state and their changes during the transition from the ground electronic state to excited ones. Transition energies to the first singlet state are obtained for the first time; the degree of stability of magnetic properties with temperature is evaluated in a wide range. The limiting number of silicon atoms, which corresponds to the disappearance of the cluster magnetic moment is found. The non-empirical calculation is compared with the data of the elecron density functional method in its different variants. The presence of iron-silicon clusters in the substance can be the reason for a local alteration of the magnetic field.

DOI: 10.1134/S0022476615010011
																								



2.
CHOICE OF QUANTUM CHEMICAL METHODS AND THE CALCULATION OF THE STRUCTURE, DIPOLE MOMENT, AND POLARIZABILITY OF PHOSPHORYL COMPOUNDS IN THE GAS PHASE

A. V. Lebedev
Closed Joint-Stock Company “SPETSPRIBOR”, Tula, Russia
Keywords: фосфорильные соединения, квантово-химический расчет, длина связи, валентный угол, дипольный момент, поляризуемость, phosphoryl compounds, quantum chemical calculation, bond length, bond angle, dipole moment, polarizability

Abstract >>
Molecules of phosphoryl compounds (H 3PO, HF 2PO, F 3PO, Cl 3PO, CH 3POF 2, CH 3POCl 2, and (CH 3) 3PO) are calculated at the Hartree-Fock, density functional theory with the B3LYP functional, and Möller-Plesset second order perturbation theory levels with different basis sets. Based on the calculation results and the comparison with the existing experimental data, methods and basis sets providing the calculation of the structures, dipole moments, and polarizabilities of phosphoryl compounds with high accuracy and low costs of computational resources are selected.

DOI: 10.1134/S0022476615010023
																								



3.
TO THE QUESTION ON THE MOLECULAR STRUCTURE OF THE ISOBUTANOL MOLECULE

Ch. O. Kadzhar, G. I. Ismailzade, M. R. Menzeleev, I. Z. Movsumov
Institute of Physics, National Academy of Sciences of Azerbaijan, Azerbaijan, Baku
Keywords: структура, конформация, изобутанол, микроволновая спектроскопия, вращательные постоянные, структурные параметры, structure, conformation, isobutanol, microwave spectroscopy, rotational constants, structural parameters

Abstract >>
The probable structure of the isobutyl alcohol molecule (СН3)2СНСН2ОН is calculated in four most stable conformations. The basic principles of obtaining an adaptive structure of the molecule are presented. The sets of interatomic distances, bond angles and calculated rotational constants are given for each of the conformations.

DOI: 10.1134/S0022476615010035
																								



4.
A QUANTUM CHEMICAL STUDY OF THE STRUCTURE OF DODECASILSEQUIOXANE H 12Si 12O 18

N. P. Rusakova1, V. V. Turovtsev1,2, Yu. D. Orlov1
1Tver State University, Tver, Russia
2Tver State Medical Academy, Tver, Russia
Keywords: простые эфиры сульфоксиловой кислоты, индуктивный эффект, квантовая теория атомов в молекуле (QTAIM), электроотрицательность, шкала электроотрицательности, электронная плотность, эффективный заряд, функциональная группа, ethers of sulphoxylate acid, inductive effect, quantum theory of atoms in molecule (QTAIM), electronegativity, electronegativity scale, electronic density, effective charge, functional group

Abstract >>
Within the quantum theory of atoms in molecules (QTAIM) the electronic structure of sulphoxylate acid НОSОH and compounds of a homological series of ethers of sulphoxylate acid CH 3(CH 2) n ОSОH, where n ≤ 8, is studied. It is found that there is an intramolecular hydrogen bond O⋯H resulting in the formation of a cyclic structure СH 3CH 2OSOH. Qualitative relationships of the electronegativities of the groups χ( R) are obtained and the χ( R) scale is derived. The possibilities of predicting “structure-property” correlations are discussed.

DOI: 10.1134/S0022476615010047
																								



5.
INTERNAL ROTATION POTENTIAL FUNCTIONS OF AN ACRYLOYL FLUORIDE MOLECULE IN THE GROUND ( S 0) AND EXCITED ( S 1) ELECTRONIC STATES

L. A. Koroleva, V. I. Tyulin, V. K. Matveev, Yu. A. Pentin
Moscow State University, Moscow, Russia
Keywords: параметры потенциальной функции внутреннего вращения, транс- и цис-изомер, основное (S ) и возбужденное (S ) электронные состояния, internal rotation potential function parameters, trans- and cis-isomer, ground (S ) and excited (S ) electronic states

Abstract >>
Structural parameters of trans- and cis-isomers of an acryloyl fluoride molecule in the ground ( S 0) and excited ( S 1) electronic states are determined. The F(φ) function is expanded into the Fourier series. The internal rotation potential functions (IRPFs) of acryloyl fluoride in both electronic states are derived. To this end, torsional vibrational transition frequencies of both isomers of this molecule were used, which were obtained from the analysis of the vibrational structure щf a high resolution UV spectrum of acryloyl fluoride vapor with regard to the geometry and energy difference (Δ H) of the isomers. The IRPF parameters V n of this molecule in the ( S 0) state, which were derived based on the transition frequencies of torsional vibrations from the vibrational structure of the high resolution UV spectrum and the IR fourier spectrum coincided.

DOI: 10.1134/S0022476615010059
																								



6.
MULTINUCLEAR NMR STRUCTURAL STUDY OF NOVEL Оі-IMINOPHOSPHONATE AND PHOSPHINE OXIDE DERIVATIVES

A. Wahbi, H. Slimani, S. Touil
University of Carthage, Jarzouna, Tunisia
Keywords: C NMR , P NMR , H NMR , g-iminophosphonates, phosphine oxides, E/Z isomerism, C NMR , P NMR , H NMR , g-iminophosphonates, phosphine oxides, E/Z isomerism

Abstract >>
We report for the first time the synthesis of γ-iminophosphonates and phosphine oxides from the acid-catalysed reaction of primary amines with γ-phosphonylketones. The full characterization of these compounds through their 1H, 31P, and 13C NMR spectra indicates that they are obtained as a mixture of Z and E isomers. An unambiguous method for the assignment of these configurations, based on the 13C chemical shifts of C2 carbon atoms in the a position with respect to the C=N double bond is used. The 31P chemical shifts are also of diagnostic importance in assigning the Z and E configurations. Indeed, the phosphorus atom is found to resonate at a slightly higher field in Z isomers.

DOI: 10.1134/S0022476615010060
																								



7.
CRYSTAL STRUCTURE, SPECTROSCOPY, AND THEORETICAL CALCULATIONS OF TWO BIS(BENZIMIDAZOLYL)BUTANE DERIVATIVES

G.-Y. Li1, J.-S. Hu1, Y.-F. Liu2, G.-H. Cui1
1Hebei United University, Tangshan, P. R. China
2Henan Normal University, Xinxiang, P. R. China
Keywords: coordination polymer, benzimidazole, crystal structure, DFT, NBO

Abstract >>
Two ligands for coordination compounds incorporating benzimidazole moieties, namely 1,1'-butane-1,4-diylbis(5,6-dimethyl-1H-benzimidazole) and 1,1'-butane-1,4-diylbis(1H-benzimidazole), are synthesized and then characterized both experimentally and theoretically. Their structures are studied by single crystal X-ray diffraction, UV-Vis spectroscopy, and FT-IR spectroscopy. The optimized geometries, vibrational frequencies, vertical excitation energies of the two ligands are calculated using the (TD)DFT/B3LYP/TZVP method. The calculated results reproduce the experimental data. Additional bonding information about the coordinated N atoms in the two ligands is obtained by FMO and NBO analysis to investigate the substitute-group effect on the coordination ability. The results confirm that the ligand with electron-donating methyl groups on the benzimidazole moieties has a stronger coordination ability.

DOI: 10.1134/S0022476615010072
																								



8.
MELTING OF THE WATER HEXAMER

E. D. Belega, D. N. Trubnikov, E. A. Cheremukhin
Moscow State University, Moscow, Russia
Keywords: кластеры молекул воды, плавление гексамера воды, индекс Линдемана, фазовые переходы в кластерах, изомеры кластеров воды, water molecule clusters, melting of the water hexamer, Lindemann index, phase transitions in clusters, water cluster isomers

Abstract >>
Results are presented for a molecular dynamics simulation of melting of the water hexamer from three-dimensional configurations (the book, cage, and prism isomers). The interactions between water molecules are described using two rigid potentials-TIP4P and TIP5P. The isomer geometry is determined using the connectivity matrix of the H-bond network graph. It is found in a numerical experiment that the Lindemann index, which shows the fluctuations in the length of intermolecular bonds, behaves similarly for all the studied initial isomers of the cluster. The melting of the cluster is found to depend on the interaction potential used in the study. For the cluster’s full energy, regions are identified which can be attributed to the premelting phase, which is dominated by the book isomer for TIP4P and ring isomer for TIP5P. The energy region attributed to the quasi-liquid phase of the cluster is shown to be characterized by isomers with ring and linear structures for both of the potentials.

DOI: 10.1134/S0022476615010084
																								



9.
THERMODYNAMIC AND STRUCTURAL CHARACTERISTICS OF AQUEOUS ALKANOLAMINE SOLUTIONS

A. G. Titova1, M. A. Krest’yaninov2, A. M. Zaichikov1
1Ivanovo State University of Chemistry and Technology, Ivanovo, Russia
2Krestov Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo, Russia
Keywords: внутреннее давление, межмолекулярные взаимодействия, термодинамические и структурные характеристики водных растворов аминоспиртов, вода, апротонные амиды, internal pressure, intermolecular interactions, thermodynamic and structural characteristics of aqueous alkanolamine solutions, water, aprotic amides

Abstract >>
Thermodynamic characteristics are calculated for aqueous alkanolamine solutions that are obtained by substituting alkyl radicals for the protons in the amino group of monoethanolamine and form no hydrogen bond networks. Patterns are found in the variations of the structural properties of the mixtures. A correlation is observed between the entropy and enthalpy characteristics of the water-alkanolamine systems with excess packing coefficients, suggesting that the structural and energy properties of aqueous solutions of these alkanolamines are determined by universal interactions. The concentration curves for the structural and thermodynamic characteristics of the systems are symbatic with the data on water-aprotic amide mixtures. Explanations of this behavior are discussed by comparing the results with the previous data on aprotic amide solutions.

DOI: 10.1134/S0022476615010096
																								



10.
STRUCTURE OF DIMERS OF GLYCYRRHIZIC ACID IN WATER AND THEIR COMPLEXES WITH CHOLESTEROL: MOLECULAR DYNAMICS SIMULATION

M. V. Zelikman1,2, A. V. Kim1,2, N. N. Medvedev1,2, O. Yu. Selyutina1,2, N. E. Polyakov2
1Novosibirsk State Research University, Novosibirsk, Russia
2Voevodskii Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: молекулярно-динамическое моделирование, водные растворы, глицирризиновая кислота, холестерин, структура ассоциатов, механизм гость, хозяин, molecular dynamics simulation, aqueous solutions, glycyrrhizic acid, cholesterol, structure of associates, guest-host mechanism

Abstract >>
The molecular dynamics simulation of dimers of glycyrrhizic acid (GA) arising from the spontaneous meeting of two GA molecules in water is performed. Shown that the molecules in the dimer are quite close to each other, there is no place between them where another molecule (including water molecule) could fit. The relatively stable structures of dimers are found, which are characterized by the specific values of angles between the terpene skeletons of GA molecules and sugar ends. Due to thermal motion, the spontaneous transitions between these structures occur. The insertion of a molecule of cholesterol in the solution showed that the associates formed from two GA molecules and one cholesterol molecule are, as a rule, one of stable GA dimers with the attached cholesterol molecule.

DOI: 10.1134/S0022476615010102
																								



11.
ON THE MUTUAL SOLUBILITY IN MMOO 4-LNVO 4 SYSTEMS, WHERE M = CA, CD, SR, BA, PB, LN = Y, SC, CE-LU

V. D. Zhuravlev1, O. G. Reznitskikh2, V. G. Bamburov1
1Institute of Solid State Chemistry, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
2Institute of High Temperature Electrochemistry, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
Keywords: гетеровалентные взаимозамещения, твердые растворы, энтальпия смешения, циркон, шеелит, heterovalent mutual substitutions, solid solutions, mixing enthalpy, zircon, scheelite

Abstract >>
The factors determining the solubility in MMoO 4(scheelite)-LnVO 4(zircon) systems, where M = Ca, Cd, Sr, Ba, Pb, Ln = Y, Sc, La-Lu, are analyzed. It is shown that primary solid solutions based on REE vanadates are absent due to a high (above 36 kJ/mol) enthalpy of polymorphic scheelite → zircon transition. For solid solutions based on bivalent metal molybdates, the zircon → scheelite transition has a lower enthalpy of 16-22.3 kJ/mol. The differences in bond ionicity in MoO 4 2- and VO 4 3- anions and interatomic distances in MO 8 and LnO 8 polyhedra restrict mutual solubility of the initial compounds, but are not the cause of its asymmetry.

DOI: 10.1134/S0022476615010114
																								



12.
FEATURES OF ANIONIC ISOMORPHISM IN FLUORIDE BORATES

S. V. Rashchenko1,2, V. V. Bakakin3, S. G. Kozlova2,3,4, T. B. Bekker1,2, P. P. Fedorov5
1Sobolev Institute of Geology and Mineralogy, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk State Research University, Novosibirsk, Russia
3Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
4Belgorod State Technological University, Belgorod, Russia
5Prokhorov Institute of General Physics, Russian Academy of Sciences, Moscow, Russia
Keywords: анионный изоморфизм, ортобораты, фтор, anionic isomorphism, orthoborates, fluorine

Abstract >>
In the work the structures of fluoride borates demonstrating the substitution with the stoichiometry (BO 3) 3- ↔ 3F - are analyzed and the specific role of tetrahedral anionic [X 4] 4- groups is revealed in this substitution. The possibility of the F-F interaction in [F 4] 4- groups uncharacteristic of ionic crystals is confirmed by ab initio quantum chemical simulation of the crystal structure of Ba 4- xSr 3+ x(BO 3) 4- yF 2+3 y.

DOI: 10.1134/S0022476615010126
																								



13.
A NEW PENTACOORDINATE POLYMERIC COPPER(II) COMPLEX WITH 2-AMINO-2-METHYL-1,3-PROPANDIOL: STRUCTURAL INVESTIGATIONS USING XRD AND DFT

G. Abbas1, A. Hassan2, A. Irfan3, M. Mir1, Mariya-al-Rashida4, G. Wu5
1Interdisciplinary Research Centre in Biomedical Materials, COMSATS Institute of Information Technology, Lahore 54700, Pakistan
2Institute of Chemistry, University of the Punjab, Lahore, Pakistan
3King Khalid University, Abha 61413, P.O. Box 9004, Saudi Arabia
4A Chartered University, Ferozepur Road-54600, Lahore, Pakistan
5Jilin University, 2699 Qianjin Street, Changchun 130012, P. R. China
Keywords: copper complex, frontier molecular orbitals, absorption spectrum, density functional theory, time dependent density functional theory

Abstract >>
A novel mononuclear copper complex [Cu(NH 2mpdH)(NH 2mpd) 2Cl] ( 1) is synthesized from 2-amino-2-methyl-1,3-propandiol (ampdH 4). The crystal structure of (1) is determined using X-ray diffraction studies. The copper complex crystallizes in the triclinic space group P-1(2) with a = 6.10.48(4) Å, b = 10.0915(7) Å, c = 10.9249(9) Å, α = 95.925(6)°, β = 101.830(6)°, γ = 90.637(5)°, V = 649.53(95) Å 3 and Z = 2. The central copper(II) atom in ( 1) is coordinated by three oxygen and two nitrogen atoms possessing a five-coordinate distorted square pyramidal geometry arranged in a one dimensional polymeric chain. The ground state geometry of the mononuclear copper complex is optimized using the DFT/B3LYP/6-31G** (LANL2DZ) level of theory. Intra-molecular charge transfer is investigated based on the frontier molecular orbitals. The distribution pattern of the highest occupied molecular orbital and the lowest unoccupied molecular orbital is studied. Absorption spectra are computed using The time dependent density functional theory (TDDFT). The absorption wavelengths are calculated using different functionals, i.e., BHandHLYP, CAM-B3LYP, and LC-BLYP.

DOI: 10.1134/S0022476615010138
																								



14.
MOLECULAR AND CRYSTAL STRUCTURE OF IRON(III) AND NICKEL(II) COMPLEXES WITH 1'-PHTHALAZINYLHYDRAZONES OF HETEROCYCLIC CARBONYL COMPOUNDS

L. D. Popov1, S. I. Levchenkov2, I. N. Shcherbakov1, G. G. Aleksandrov3, Z. A. Starikova†4, V. V. Lukov1, V. A. Kogan1
1Faculty of Chemistry, Southern Federal University, Rostov-on-Don, Russia
2Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
3Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
4Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
Keywords: гидразоны, координационные соединения, рентгеноструктурный анализ, hydrazones, coordination compounds, single crystal X-ray diffraction analysis

Abstract >>
The structures of iron(III) and nickel(II) complexes with the composition [FeL 2]Cl×H 2O ( 1) and [Ni(HL 2')]×DMSO×0.5H 2O ( 2), where L and HL' are monodeprotonated residues of 1'-phthalazinylhydrazones of 2-acetyl benzimidazole and 1-phenyl-3-methyl-4-formyl-5-hydroxypyrazole respectively, are determined using single crystal X-ray diffraction analysis. Both compounds crystallize in the monoclinic symmetry. The Fe(III) and Ni(II) ions in the complexes have octahedral N 6 and N 4O 2 donor environments respectively. Due to intermolecular hydrogen bonds, the molecules of the complexes form corrugated (complex 1) and linear (complex 2) molecular chains in the crystal.

DOI: 10.1134/S002247661501014X
																								



15.
CRYSTAL STRUCTURE OF THE COORDINATION POLYMER [Cu 2( S-mal) 2(bpy) 2(H 2O)]В·2.5H 2O

M. S. Zavakhina1,2, D. G. Samsonenko1,2, V. P. Fedin1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: медь, координационные полимеры, металл-органические каркасы, хиральные комплексы, яблочная кислота, copper, coordination polymers, metal-organic frameworks, chiral complexes, malic acid

Abstract >>
In the interaction of basic copper carbonate with optically pure malic acid and 4,4'-bipyridine [Cu 2( S-mal) 2(bpy) 2(H 2O)]×2.5H 2O (1) is obtained. The structure of the metal-organic coordination polymer is unique for this class of compounds, which is established by the single crystal X-ray diffraction analysis using synchrotron radiation.

DOI: 10.1134/S0022476615010151
																								



16.
EFFECT OF THE NATURE OF NON-BRIDGING DONOR ATOMS ON THE STRUCTURE AND MAGNETIC PROPERTIES OF BINUCLEAR COPPER(II) COMPLEXES WITH HETEROCYCLIC AZOMETHYNE LIGANDS

S. I. Levchenkov1, I. N. Shcherbakov2, L. D. Popov2, A. I. Uraev2, K. Yu. Suponitskii3, A. A. Zubenko4, A. M. Ionov2, V. A. Kogan2
1Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
2Southern Federal University, Rostov-on-Don, Russia
3Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
4North-Caucasian Zonal Research Veterinary Institute, Novocherkassk, Russia
Keywords: азометины, комплексные соединения, рентгеноструктурный анализ, магнетохимия, обменное взаимодействие, теория функционала плотности, azomethines, complex compounds, X-ray crystallographic analysis, magnetochemistry, exchange interaction, density functional theory

Abstract >>
Pyrazolate bridging binuclear copper(II) complex with a heterocyclic azomethyne ligand (a condensation product of 1,3-diaminopropanol-2 with 1-phenyl-3-methyl-4-formyl-5-mercaptopyrazole) is synthesized and structurally characterized. The structure of the complex is compared with the structure of its pyrazolone analogue. It is shown that for the 2 J calculation the use of the previously optimized geometry rather than the geometry from the XRD data results in better agreement with the magnetochemical experiment.

DOI: 10.1134/S0022476615010163
																								



17.
STRUCTURE OF A NEW BINUCLEAR COMPLEX OF TUNGSTEN [W 2S 4Cl 2(dppe) 2]В·2CH 3CN

S. B. Artemkina1,2, A. Yu. Ledneva1, D. A. Piryazev1, A. V. Virovets1, Yu. V. Mironov1, V. E. Fedorov1,2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: вольфрам, сера, биядерный комплекс, синтез, кристаллическая структура, КР спектр, tungsten, sulfur, binuclear complex, synthesis, crystal structure, Raman spectrum

Abstract >>
In the reaction of (Et 4N) 2[W 2S 4Cl 4] with 1,2-bis(diphenylphosphino)ethane in acetonitrile a new binuclear complex of tungsten(V) [W 2S 4Cl 2(dppe) 2]×2CH 3CN is obtained. Its crystal structure is solved in the triclinic space group P-1 with the following unit cell parameters a = 10.1202(16) Å, b = 11.758(2) Å, c = 12.648(2) Å, α = 104.324(5)°, β = 106.469(5)°, γ = 97.587(5)°, V = 1364.9(4) Å 3, Z = 1, with the final refinement parameters R 1 = 0.0545, wR 2 = 0.1053. The work describes the synthesis, crystal structure, and Raman spectrum of the [W 2S 4Cl 2(dppe) 2]×2CH 3CN complex.

DOI: 10.1134/S0022476615010175
																								



18.
CRYSTAL STRUCTURES AND CHARACTERIZATION OF TWO ONE–DIMENSIONAL COORDINATION POLYMERS CONTAINING Ln3+ IONS AND ANTHRANILATE (C7H6NO2) ANIONS

S. Hussain1, I.U. Khan1, W.T.A. Harrison2, M.N. Tahir3, S. Ahmad4
1Government College University, Lahore, 54000, Pakistan
2University of Aberdeen, Aberdeen AB24 3UE, Scotland
3University of Sargodha, Sargodha, Pakistan
4University of Engineering and Technology, Lahore, Pakistan
Keywords: cerium, praseodymium, anthranilate anion, synthesis, crystal structure, one dimensional coordination polymer

Abstract >>
The syntheses, crystal structures and characterization (IR, TGA/DSC) of the isostructural one-dimensional coordination polymers [Ce(C 7H 6NO 2) 3] n ( 1) and [Pr(C 7H 6NO 2) 3] n ( 2) are described. The metal ions adopt distorted capped square anti-prismatic MO 9 coordination geometries. The anthranilate ligands bridge the metal ions in bridging-bidentate (O, μ 2-O') mode to generate [010] chains in the crystal and each ligand features an intramolecular N-H⋯O hydrogen bond. It is notable that two very similar, but crystallographically distinct chains appear in the unit cell. Crystal data: 1, C 21H 18CeN 3O 6, M r = 548.51, monoclinic, P2 1/ c (No. 14), a = 25.0476(10) Å, b = 7.4924(2) Å, c = 24.6366(7) Å, β = 119.424(1)°, V = 4027.1(2) Å 3, R( F) = 0.037, wR( F 2) = 0.068. 2, C 21H 18N 3O 6Pr, M r = 549.29, monoclinic, P2 1/ c (No. 14), a = 25.0077(13) Å, b = 7.4497(3) Å, c = 24.6063(12) Å, β = 119.392(2)°, V = 3994.1(3) Å 3, R( F) = 0.031, wR( F 2) = 0.068.

DOI: 10.1134/S0022476615010187
																								



19.
STEREOCHEMISTRY OF THE CITRATE ANION IN COMPOUNDS CONTAINING GUANIDINIUM AND CITRATE IONS

E. B. Miminoshvili1, L. A. Beridze2
1Georgian Technical University, Tbilisi, Georgia
2Tbilisi State Medical University, Tbilisi, Georgia
Keywords: комплексные соединения, структурный анализ, переходные металлы, гуанидин, цитрат, complex compounds, structural analysis, transition metals, guanidine, citrate

Abstract >>
An analysis is presented for the results obtained in the studies initiated by A. E. Shvelashivili, Corresponding Member, Academy of Sciences of Georgia, and continued by us after he has passed away. The studies are focused on guanidinium and citrate ion containing compounds. It is found that protonation delocalizes the π bond and equalizes the С-N bonds in the guanidine grouping and that the doubly or triply deprotonated citric acid anion in complex compounds acts both as a bi- and tridentate ring-forming ligand.

DOI: 10.1134/S0022476615010199
																								



20.
CRYSTAL AND MOLECULAR STRUCTURE OF BENZOAZA-12-CROWN-4 HYDROCHLORIDE

V. N. Glushko1, N. Yu. Sadovskaya1, L. I. Blokhina1, I. V. Anan'ev2
1State Scientific Research Institute of Chemical Reagents and High Purity Chemical Substances, Moscow, Russia
2Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
Keywords: рентгеноструктурный анализ, краун-эфиры, бензоаза-12-краун-4, X-ray crystallographic analysis, crown ethers, benzoaza-12-crown-4

Abstract >>
The X-ray crystallographic analysis of benzoaza-12-crown-4 hydrochloride crystals is performed for the first time: space group Р1, а = 7.7497(4) Å, b = 9.2224(5) Å, c = 10.2395(5) Å, α = 99.3965(10)°, β = 101.8387(11)°, γ = 112.6470(10)°, V = 636,81(6) Å 3, Z = 2, ρ calc = 1.355 g/cm 3. The conformation of the 12-membered ring of the molecule is determined.

DOI: 10.1134/S0022476615010205
																								



21.
NOVEL MAGNETIC MATERIALS BASED ON SEMICONDUCTING 1111 PHASES: THEORY AND EXPERIMENT

V. V. Bannikov, A. L. Ivanovskii†
Institute of Solid State Chemistry, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
Keywords: немагнитные полупроводниковые 1111 фазы, примеси замещения, новые магнитные материалы, ab initio расчеты, синтез, non-magnetic semiconducting 1111 phases, substitutional impurities, new magnetic materials, ab initio calculations, synthesis

Abstract >>
A brief review of theoretical and experimental studies devoted to the design of novel magnetic materials based on non-magnetic semiconductor phases with the ZrCuSiAs structure type (such as LaCuSO, LaCuSeO, LaZnAsO, YZnAsO, or SrAgSeF) by doping their sublattices with magnetic and non-magnetic substitutional impurities is presented. Using the results of ab initio calculations of the band structure, we discuss the possibility of obtaining new magnetic semiconductors, magnetic metals and half-metals, and also gapless magnetic semiconductors and bipolar magnetic semiconductors based on the 1111 phases. The available experimental data on the synthesis and properties of materials based on semiconducting 1111 phases doped with atoms of alkali-earth and magnetic 3 d metals are discussed.

DOI: 10.1134/S0022476615010217
																								



22.
PHASE COMPOSITION OF THIN SILICON CARBONITRIDE FILMS OBTAINED BY PLAZMA ENDANCED CHEMICAL VAPOUR DEPOSITION USING ORGANOSILICON COMPOUNDS

N. I. Fainer, V. I. Kosyakov
Nikolaev Institute of Inorganic Chemistry, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: карбонитрид кремния, тонкие пленки, гексаметилдисилазан, плазмохимическое осаждение, РФА с использованием СИ, кристаллические фазы семейства О±-Si C N , silicon carbonitride, thin films, hexamethyldisilazane, plasma chemical deposition, XRD-SR, crystalline phases of the О±-Si C N family

Abstract >>
High-temperature silicon carbonitride films are synthesized by plasma decomposition of gas mixtures of 1,1,1,3,3,3-hexamethyldisilazane (HMDS) (the synonym used by IUPAC bis(trimethylsilyl) amine) with ammonia or helium in the temperature range of 673-1273 K. It is shown that silicon carbonitride films, obtained in high temperature processes of the plasma decomposition of organosilicon compounds, are nanocomposite. In their amorphous matrix the crystals belonging to the phases of the α-Si 3- nC n N 4 family and impurity graphite are embedded. To clarify the previously obtained data by means of the X-ray diffractometry using synchrotron radiation, they are compared with the published results of modeling the structure of these phases. It is shown that nanocrystals belonging to the phases of α-Si 3N 4, α-Si 2CN 4, α-SiC 2N 4, and α-C 3N 4 are present in the films. An increase in the ammonia concentration in the initial gas mixture causes a decrease in the film hardness from 24 GPa to 16 GPa due to the increased content of α-Si 3N 4 and α-Si 2CN 4 nanocrystals having a lower hardness compared to α-C 3N 4 and α-SiC 2N 4.

DOI: 10.1134/S0022476615010229
																								



23.
CRYSTAL STRUCTURE OF THE COPPER(I) COMPLEX Cu(py–Clan)(PPh3)I

A.D. Khalaji1, K. Jafari2, K. Fejfarova3, M. Dusek3
1Golestan University, Gorgan, Iran
2Shahrood University of Technology, Shahrood, Iran
3Institute of Physics of the ASCR, Prague, Czech Republic
Keywords: copper(I) complex, Schiff base, synthesis, crystal structure, tetrahedral

Abstract >>
A mixed ligand copper(I) Schiff base complex [Cu(py-Clan)(PPh 3)I], where py-Clan = 4-chlorophenylpyridine-2-ylmethyleneamine, is synthesized and structurally characterized by single crystal X-ray crystallography. In this complex, the copper(I) ion is in a distorted four-coordinate tetrahedral geometry. The Schiff base py-Clan ligand acts as a chelating ligand and coordinates to the copper center via two nitrogen atoms. The [Cu(py-Clan)(PPh 3)I] complex crystallizes in the monoclinic space group P2 1/ c with unit cell parameters: a = 10.3339(12), b = 34.524, c = 8.3940 Å, β = 114.759(8)°, V = 2719.4(5) Å 3 and Z = 4.

DOI: 10.1134/S0022476615010230
																								



24.
CRYSTAL STRUCTURE OF A ПЂ COMPLEX OF AgBF 4 WITH 2-ALLYL-5-PHENYL-2 Н-TETRAZOLE OF THE COMPOSITION [Ag(C 10H 10N 4)(BF 4)]

Yu. I. Slyvka
Franko National University of Lviv, Lviv, Ukraine
Keywords: серебро(I), ПЂ-комплекс, тетразол, кристаллическая структура, silver(I), ПЂ complex, tetrazole, crystal structure

Abstract >>
By the interaction of AgBF 4 with 2allyl-5-phenyl-2 Н-tetrazole (2 aphet) in the ethanol solution, a π complex of [Ag(2 aphet)(BF 4)] is obtained which is studied using single crystal X-ray diffraction.

DOI: 10.1134/S0022476615010242
																								



25.
CRYSTAL STRUCTURE OF bis[1-{(3,5-DIMETHYL-1 H-PYRAZOL-1-YL)METHYL}-3,5-DIMETHYL-1 H-PYRAZOL-2-IUM] HEXACHLOROURANATE(IV): [H 2C(3,5-Me 2pz)(3,5-Me 2pzH)] 2[UCl 6]

J. M. Carretas1, J. Cui1, A. Cruz1, I. C. Santos1,2, J. Marçalo1
1Centro de CiГЄncias e Tecnologias Nucleares, Lisboa, Bobadela LRS, Portugal
2Centro de QuГ­mica Estrutural, Lisboa, Portugal
Keywords: uranium, bis(3,5-dimethylpyrazol-1-yl)methane, pyrazolium, crystal structure, short contacts

Abstract >>
The X-ray diffraction study of a single crystal with the composition [H 2C(3,5-Me 2pz)(3,5-Me 2pzH)] 2[UCl 6] (1) is performed. This compound is the product of an attempted synthesis of a bis(pyrazolyl)methane complex of uranium(IV) obtained by the reaction of UCl 4 with bis(3,5-dimethylpyrazol-1-yl)methane in THF. 1 crystallizes in the space group P-1 of the triclinic system: a = 9.6616(2) Å, b = 9.6946(2) Å, c = 10.7314(2) Å, α = 107.6210(10)°, β = 115.5600(10)°, γ = 99.6710(10)°, V = 810.45(3) Å 3, Z = 1, d calc = 1.765 g/cm 3, μ = 5.528 mm -1, R 1 = 0.0249. The structural unit consists of two separated [H 2C(3,5-Me 2pz)(3,5-Me 2pzH)] + cations and a UCl 6 2- anion. In the solid state structure of 1 several short intermolecular N-H⋯N and C-H⋯Cl contacts are identified suggesting the presence of hydrogen bonds.

DOI: 10.1134/S0022476615010254
																								



26.
STRUCTURE OF 3,3:6,6-DIBUTANO-3a-METHYL-6a-PHENYLTETRAHYDROFURO[3,2-b]FURAN-2,5-DIONE

N. F. Kirillov1, P. A. Slepukhin2, E. A. Nikiforova1
1Perm State National Research University, Perm, Russia
2Postovskii Institute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Ekaterinburg, Russia
Keywords: реакция Реформатского, тетрагидрофурофурандионы, спирофураноны, синтез, рентгеноструктурный анализ, Reformatsky reaction, tetrahydrofurofurandiones, spirofuranones, synthesis, single crystal X-ray diffraction study

Abstract >>
In the interaction of methyl 1-bromocyclopentanecarboxylate with zinc and 1-phenylpropan-1,2-dione, 3,3:6,6-dibutano-3 a-methyl-6 a-phenyltetrahydrofuro[3,2- b]furan-2,5-dione is synthesized and its structure is determined by single crystal X-ray diffraction study.

DOI: 10.1134/S0022476615010266
																								



27.
MOLECULAR AND CRYSTAL STRUCTURE OF (1 R,5 S)-8-OXO-1,5,6,8-TETRAHYDRO-2 H-1,5-METHANOPYRIDO[1,2- a][1,5]DIAZOCINE-3(4 H)-CARBOXAMIDE AND (1 R,5 S)-8-OXO-1,5,6,8-TETRAHYDRO-2 H-1,5-METHANOPYRIDO[1,2- a][1,5]DIAZOCINE-3(4 H)-THIOCARBOXAMIDE

K. Yu. Suponitskii1, I. P. Tsypysheva2, A. V. Koval'skaya2
1Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
2Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa, Russia
Keywords: (-)-цитизин, рентгеноструктурный анализ, (-)-cytisine, single crystal X-ray diffraction study

Abstract >>
The molecular and crystal structure of (1 R,5 S)-8-oxo-1,5,6,8-tetrahydro-2 H-1,5-methanopyrido[1,2- a][1,5]diazocine-3(4 H)-carboxamide and (1 R,5 S)-8-oxo-1,5,6,8-tetrahydro-2 H-1,5-methanopyrido[1,2- a][1,5]diazocine-3(4 H)-thiocarboxamide are determined.

DOI: 10.1134/S0022476615010278
																								



28.
SOLVOTHERMAL SYNTHESES, CRYSTAL STRUCTURE, AND PHOTOLUMINESCENT PROPERTIES OF TWO Cu(I) COORDINATION POLYMERS CONSTRUCTED BY BISIMIDAZOLE LIGANDS

K.-H. Wang1, M.-C. Zhu2, D.-L. Wang1, J. Bai1, Y. Liu1, G. Xin1, T.-C. Li1, D.-Y. Hou1, E.-J. Gao2
1Anshan Normal University, Anshan, P. R. China
2Shenyang University of Chemical Technology, Shenyang, P. R. China
Keywords: Cu(I) coordination polymers, crystal structure, bisimidazole ligands

Abstract >>
Two Cu(I) coordination polymers {[Cu 2(bibp) 2]×bdc×3H 2O} n ( 1) and {[Cu 3(bib) 3]×btc×5H 2O} n ( 2), where bibp = 4,4'-bis(1-imidazol-1-yl)biphenyl, H 2bdc = terephthalic acid, bib = 1,4-bis(1-imidazol-1-yl)benzene, H 3btc = benzene-1,3,5-tricarboxylic acid, are synthesized under solvothermal conditions and characterized structurally. Complex 1 crystallizes in the triclinic form with the space group P-1, and Cu(1) is two-coordinated by two N atoms of bibp, Cu(2) is three coordinated from two N atoms of bibp and one water molecule. Complex 2 crystallizes in the triclinic form with the space group P-1; the copper ions are monovalent and two-coordinated by two N atoms of bib. The bdc and btc ligands are not coordinated with Cu ions, but play important roles in the generation of a 3D supramolecular structure of complexes 1 and 2 via weak interactions respectively.

DOI: 10.1134/S002247661501028X
																								



29.
CHARACTERIZATION AND CRYSTAL STRUCTURE OF A NOVEL TETRANUCLEAR ZINC(II) COMPLEX DERIVED FROM N,N'-BIS(2-HYDROXY-5-METHOXYBENZYLIDENE)PROPANE-1,3-DIAMINE

G.-H. Sheng1, X.-S. Cheng2, Z.-L. You2, H.-L. Zhu1
1Shandong University of Technology, Shandong, P. R. China
2Liaoning Normal University, Liaoning, P. R. China
Keywords: Schiff base, zinc complex, tetranuclear complex, crystal structure

Abstract >>
A novel tetranuclear zinc(II) complex [Zn 4Br 4L 2(H 2L)], where L and H 2L are the dianionic and zwitterionic forms of N, N'-bis(2-hydroxy-5-methoxybenzylidene)propane-1,3-diamine, is prepared and structurally characterized by elemental analysis, IR spectrum, and single crystal X-ray crystallography. The complex crystallizes in the monoclinic space group C2/ c, with unit cell dimensions a = 38.338(2) Å, b = 10.5662(5) Å, c = 17.4607(8) Å, β = 113.767(2)°, V = 6473.3(6) Å 3, Z = 4, R 1 = 0.0686, and wR 2 = 0.1752. The inner Zn atoms are five-coordinated in a square pyramidal geometry, and the outer Zn atoms are four-coordinated in a tetrahedral geometry. The intramolecular Zn⋯Zn distance is 3.103(1) Å.

DOI: 10.1134/S0022476615010291