Synthesis, Crystalline Structure, and Spectra of 3,3-Dimethyl-1-(3-methyl-1-phenylpyrazol-5-onylidene-4)-1,2,3,4-tetrahydroisoquinoline

3,3-Dimethyl-1-(3-methyl-1-phenylpyrazol-5-onylidene-4)-1,2,3,4-tetrahydroisoquinoline has been synthesized and its crystalline and molecular structures determined. It was found by IR and electronic absorption spectroscopic methods that the structure of this compound is not changed in solutions.     

Synthesis and crystal structure of divaleratobis(nicotinamide)copper(II)

A copper(II) valerate complex with nicotinamide (L) [CuL₂(C₄H₉COO)₂] (I) has been synthesized and studied by IR spectroscopy and thermogravimetry. The crystal structure has been determined. The crystals of 1 are monoclinic, a = 11.297(1) Å, b = 6.666(1) Å, c = 16.873(2) Å, b = 108.50(1)°, V = 1204.9(3) ų, Z = 2, space group P2₁/c. The structural units of the crystal of I are centrosymmetric tetragonal bipyramidal (4+2) complex molecules. The equatorial positions of the bipyramid are occupied by trans-arranged pairs of O (Cu-O, 1.973 Å) and N (Cu-N, 2.006 Å) atoms, and the axial positions are occupied by the second O atoms of the valerate anions located at longer distances (Cu-O, 2.506 Å). The supramolecular associates formed in the crystal are layers of hydrogen-bonded complexes. The disordered hydrocarbon “tails” of the valerate groups point toward the interlayer space.     

New method for the synthesis of cage and polymeric metallosiloxanes

Cage organometallosiloxanes were synthesized according to a new procedure using monomeric organoalkoxysilanes as the starting compounds. The latter were subjected to hydrolysis immediately before the exchange reaction of sodium silanolate with metal halides. Difficultly accessible metallovinylsiloxanes, metallomethylsiloxanes, and metallosiloxanes containing a functional group in the organic radical at the silicon atom can be readily prepared according to the method proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2530–2532, December, 1998.     

Ionic Mobility, Phase Transitions, and Superionic Conduction in Solid Solutions (100 ? x)PbF2-xZrF4 and Crystals K2ZrF6, (NH4)2ZrF6, KSnZrF7, and M(NH4)6Zr4F23 (M = Li, Na)

Methods of (¹⁹F, ¹H) NMR and impedance spectroscopy are used to investigate the internal mobility and ionic conduction in solid solutions arising in the system PbF₂-ZrF₄ and polycrystals KSnZrF₇, Li(Na)(NH₄)₆Zr₄F₂₃, and M₂ZrF₆ (M = K, NH₄). Factors responsible for the form of ionic motions and their energetics at 170–550 K are considered. It is established that the phase transitions in these compounds are connected with the crystal transition to a superionic state and that the high ionic (superionic) conductivity of beta phases is due to the diffusion of fluoride ions, ammonium cations, and possibly alkali metal cations. The obtained data testify to a substantial role of chainlike aggregation of anionic groupings and a variableness of structural mechanisms of formation of such chains in fluorozirconates for the development of translational diffusion in these compounds.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 573–582.Original Russian Text Copyright © 2005 by Kavun, Uvarov, Slobodyuk, Goncharuk, Kotenkov, Tkachenko, Gerasimenko, Sergienko.     

Isomorphous inclusions of silicon, aluminum, and titanium in the germanate zeolite IPC-3

The zeolite IPC-3, isomorphous with germanate zeolite ASU-16, and its silicon, aluminum, and titanium analogs, were obtained in the presence of 1,6-diaminohexane as a template. It is possible to incorporate selectively the elements in different crystallographic positions, determined by the nature of the element, particularly its valency and its coordination number with respect to oxygen. Silicon takes tetrahedral positions in the IPC-3 lattice, Al either tetrahedral or octahedral positions, and Ti octahedral positions. Small amounts of the lithium cations facilitate tetrahedral coordination and increase the Al content in IPC-3. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 4, pp. 246–251, July–August, 2006.     

μ-Oxo-Bis(Tetraphenylantimony): Synthesis,Structure, and Reactions

Heating of a solution of pentaphenylantimony in toluene in atmospheric oxygen affords -oxo-bis(tetraphenylantimony) (I) in a 63% yield. The latter compound can be converted to bis(tetraphenylantimony) carbonate or phthalate by the action of carbon dioxide or phthalic anhydride, respectively. According to X-ray diffraction data, the antimony atoms in compound Ihave a distorted trigonal-bipyramidal coordination (Sb–O 2.0050(4) Å, the SbOSb angle 151.71(9)°). The molecule of bis(tetraphenylantimony) phthalate is composed of two equal fragments, and its Sb atoms also have trigonal-bipyramidal coordination (Sb–O 2.2421(8) Å; Sb–C 2.176(1), 2.115(1), 2.130(1), and 2.137(1) Å).     

Synthesis and Spectroscopic Study of Iron(III) and Copper(II) Chloride Complexes with 2-(3,3-Dimethyl-1,2,3,4-tetrahydroisoquinolylidene-1)-5,5-dimethyl-2,3,5,6-tetrahydroimidazo[2,1-a]isoquinoline-3-one (L). The Crystal Structure of L

Complexes of Fe(III) and Cu(II) chlorides with 2-(3,3,-dimethyl-1,2,3,4-tetrahydroisoquinolylidene-1)-5,5-dimethyl-2,3,5,6-tetrahydroimidazo[2,1-a]isoquinoline-3-one (L) were synthesized and studied by IR and electronic absorption spectroscopy. X-ray diffraction analysis of compound L was carried out. The molecule of L was found to crystallize in the form of cis-isomer with the proton localized on the nitrogen atom of the dihydroisoquinoline fragment.     

19F NMR study of the influence of the nature of outer-spheric cations on the dynamics of the anion sublattice in compounds MM′AF6

Dynamics of octahedral ions in crystal compounds MM′AF₆ (M, M′=Li, Na, K, Rb, Cs; A=Ge, Ti) has been studied in the temperature range 115–500 K. Types of inner motions of complex ions have been established, and their activation energies have been estimated. First-order transition has been found in compound LiRbTiF₆. Institute of Chemistry, Far-East Branch, Russian Academy of Sciences. Translated fromZhurmal Strukturnoi Khimii, Vol. 36, No. 4, pp. 697–702, July–August, 1995. Translated by L. Smolina     

Ion mobility,phase transitions,and ion transport in potassium-ammonium hexafluorozirconates

The mobility of fluoride and ammonium ions (180–480 K) in compounds K_{2? n} (NH4)_nZrF₆ (0.2 ≤ n ≤ 1.70) was investigated by ¹⁹F and ¹H NMR. Correlations have been found between the composition of the cation sublattice, the character of ion motions, and phase transition temperature in these compounds. The hightemperature modifications with n ≥ 0.85 of the compounds are characterized by translational diffusion of fluoride and ammonium ions and by uniaxial anisotropy of the ¹⁹F magnetic shielding tensor. The electrophysical characteristics of these compounds were studied in the temperature range 300–480 K.