a:2:{s:4:"TYPE";s:4:"HTML";s:4:"TEXT";s:110:"S. P. Gabuda†1, S. G. Kozlova1,2, N. B. Kompankov1, K. S. Redkina2";} 1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: водный раствор триэтиламина, фазовый переход, ЯМР Н, aqueous triethylamine solution, phase transition, Н NMR
The 1Н NMR spectra in a binary aqueous triethylamine solution are recorded with a lower critical point of the liquid-liquid phase transition. It is found that, above the critical temperature the 1Н NMR spectra of water and triethylamine molecules in the phase with a predominant content of triethylamine molecules are characterized by an inhomogeneous broadening. It can be supposed that the found broadening is due to the features of the molecular distribution at the interface.
N. V. Podberezskaya1, V. Yu. Komarov1,2, M. Yu. Kameneva1, L. P. Kozeeva1, A. N. Lavrov1 1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: кобальтаты, монокристаллы, нестехиометрия по кислороду, структурный анализ, обработка рентгендифракционных данных, структурные модели, cobaltates, single crystals, oxygen non-stoichiometry, structural analysis, X-ray diffraction data processing, structural models
Impurity-free R BaCo4O7+ x ( R = Y, Lu) crystals are grown and the evolution of their structure with varying oxygen concentration in the range 0 £ x £ 1.3 is studied. The structural features of the studied samples required to develop an extended strategy of the X-ray crystallographic experiment, which made it possible to obtain more accurate data on unit cell parameters and additional information on the features of superstructure modulation and diffuse scattering, along with the phase composition of crystalline samples. A crystal chemical analysis of the known structural models of R BaCo4O7+ x is performed and suggestions are made about possible structural changes occurring when the oxygen concentration increases up to the limit.
S. V. Borisov, N. V. Pervukhina, S. A. Magarill
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: кристаллографический анализ, катионные подрешетки, механико-волновая концепция кристаллического состояния, когерентная сборка, механизм кристаллизации, crystallographic analysis, cation sublattices, mechanical-wave concept of crystal state, coherent assembly, crystallization mechanism
By means of the mechanical-wave concept of crystal state and the crystallographic analysis the universal regularities of the crystal structure formation are determined: presudotranslational ordering of atoms within unit cells; separate ordering of different groups of atoms with the alignment of their sublattice parameters; the principle of coherent assembly a structure from stable building blocks with the local geometry and block symmetry spread on the structure formed, and so on. The crystallization mechanism is illustrated by specific structures.
V. V. Bakakin
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: катионные каркасы, темплаты, ортобораты, фторидобораты бария, фторидобораты свинца, антицеолиты, cation frameworks, templates, orthoborates, barium fluoride borates, lead fluoride borates, antizeolites
The crystallogenesis of three groups of structures of fluoride-orthoborates (and their analogs) with large cations is studied from the point of view of the current cation-framework representations. Their cation frameworks are sterically templated by rigid borate anions and are built as antizeolite structures. Cavities of channel or layered types are filled with components different their composition and configuration with the main function as charge compensators. An example of different functionalities of the identical anions are Ba3(BO3)2 and La3Ca3(BO3)5 structures. In these structures, two (BO3) types generate a cation framework, and the third type stabilizes it in ready channels (!).
A. S. Sukhikh1,2, T. V. Basova1,2, S. A. Gromilov1,2 1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University
Keywords: рентгеновская дифрактометрия поликристаллов, ориентированные образцы, тонкие пленки, индицирование, фталоцианины палладия, X-ray diffractometry of polycrystals, oriented samples, thin films, indexing, palladium phthalocyanines
An approach for the substantiated choice of the indexing procedure of a diffraction pattern is described. The technique is based on a combined use of powder X-ray diffraction data in Bragg-Brentano schemes and 2D GIXD of mainly oriented polycrystalline samples.
Ya. S. Fomenko1, A. L. Gushchin1,2, V. A. Nadolinny1, P. A. Abramov1, M. N. Sokolov1,2 1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: ванадий, дитиолатные комплексы, кристаллическая структура, спектры ЭПР, vanadium, dithiolate complexes, crystal structure, EPR spectra
The tris-chelate complex of vanadium(IV) (Bu4N)2[V(dmit)3] is prepared from VCl3 and (Bu4N)2[Zn(dmit)2] (dmit = isotrithionedithiolate C3S52-) and characterized by single crystal XRD and mass spectrometry. The complex crystallizes in the space group Pna 21 and has a distorted octahedral environment of vanadium. The complex is paramagnetic and gives a characteristic EPR spectrum in both solution and solid phase. The g factors and hyperfine interaction constants are determined.
G. I. Zharkova, I. A. Baidina, A. I. Smolentsev, P. A. Stabnikov, N. B. Morozova
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: β-иминокетонаты Pt(II), структура, летучесть, прекурсор для MOCVD, Pt(II)β-iminoketonates, structure, volatility, MOCVD precursor
A novel volatile Pt(II)b-iminoketonate complex is synthesized. b-Aminovinylketone H(i-ptac) = [CF3-C(O)-CH=C(NH2)-C(CH3)3] is used as a ligand. The XRD method is used to determine the structures of the ligand and the complex. The crystallographic data for C16H22F6N2O2Pt are as follows: a = 10.0716(4) Å, b = 10.9572(4) Å, c = 9.6322(4) Å, b = 110.9010(10)°, space group С 2/ m , Z = 2, R = 0.011. The platinum atom has a square planar coordination with two oxygen and two nitrogen atoms of two bidentately linked ketoiminate ligands in trans -position; the PtO2N2 coordination site is formed.
V. A. Vorobyev1,2, V. A. Emelyanov1,2, I. A. Baidina1, D. A. Piryazev1,2 1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: рутений, нитрозокомплексы, нитратокомплексы, амминокомплексы, отработанное ядерное топливо, рентгеноструктурный анализ, расчеты DFT, ruthenium, nitrosyl complexes, nitrato complexes, ammine complexes, spent nuclear fuel, single crystal X-ray diffraction analysis, DFT calculations
Single crystal X-ray diffraction is used to study the nitrosoruthenium mer- trinitrato complex [RuNO(NH3)2(NO3)3]. The crystallographic data for H6N6O10Ru are as follows: a = 7.6477(1) Å, b = 10.8404(2) Å, c = 24.0168(6) Å, a = b = g = 90°, V = 1991.09(7) Å3, Z = 8, d calc = 2/338 g/cm3, space group Р 212121. The structure is formed of two structurally non-equivalent uncharged mer- [RuNO(NH3)2(NO3)3] complexes. The complex crystallizes as yellow needles or orange powder belonging to the orthorhombic system. The substance is poorly soluble in water, ethanol, and acetone, stable in dark storage. The comparisons with the EXAFS data for this complex and the theoretical DFT calculations with different functionals are performed.
D. V. Bonegardt1,2, I. Yu. Il'in1, T. S. Sukhikh1,2, N. B. Morozova1 1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: иридий(I), 1,5-циклооктадиен, пентаметилциклопентадиен, рентгеноструктурный анализ, термогравиметрия, iridium(I), 1,5-cyclooctadiene, pentamethylcyclopentadiene, single crystal X-ray diffraction analysis, thermogravimetry
Volatile iridium(I) complexes [Ir(cod)Cpx] (Cpx = pentamethylcyclopentadienyl Cp*, ethylcyclopentadienyl CpEt, cod = 1,5-cyclooctadiene) are synthesized and characterized by IR and NMR spectroscopy. The [Ir(cod)Cp*] complex is a solid and the [Ir(cod)CpEt] complex is a liquid (SATP). The XRD method is used to determine the structure of the [Ir(cod)Cp*] complex: chemical formula C18H27Ir, space group P21/ с , a = 8,4418(2) Å, b = 9,4764(3) Å, c = 19.2682(5) Å, β = 96.128(1) °, V = 1532.61(7) Å3, Z = 4, d calc = 1.888 g/cm3, m = 8.697 mm-1. The cyclopentadienyl ligand is h5-type coordinated; 1,5-cyclooctadiene have a cis - cis conformation and is h4-type coordinated. The thermal properties of the complexes are studied by thermogravimetry.
A. A. Ivanov1, N. V. Kuratieva1,2, M. A. Shestopalov1,2, Yu. V. Mironov1,2 1Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia 2Novosibirsk National Research State University, Novosibirsk, Russia
Keywords: рений, кристаллическая структура, октаэдрические халькогенидные кластеры, rhenium, crystal structure, octahedral chalcogenide clusters
A cluster complex of the composition [CsK2(m3-DMF)2(m-DMF)3(DMF)4][{Re6(m3-Se)8}Br6] is obtained by the reaction of K4[{Re6(m3-Se)8}(OH)6]×8H2O with hydrobromic acid in the presence of CsBr and its subsequent crystallization by diethyl ether diffusion in a dimethylformamide solution. The compound crystallizes in the triclinic space group P , with the following unit cell parameters: a = 13.6169(3) Å, b = 14.7584(4) Å, c = 18.1573(4) Å, a = 103.332(1)°, b = 108.250(1)°, g = 97.371(1)°, V = 3286.55(14) Å3, Z = 2, d calc = 3.130 g/cm3. The crystal structure is built of [{Re6Se8}Br6]3- anionic cluster complexes and complex [CsK2(m3-DMF)2(m-DMF)3(DMF)4]3+ cations.
