Three New 1D Polymeric Zinc(II) and Cadmium(II) Azido Complexes Containing Noncoordinated Pyridine-N-oxide or 3-Picoline-N-oxide

Abstract

The interaction of pyridine-N-oxide (pyNO) and 3-picoline-N-oxide (3picNO) with zinc(II) and cadmiura(II) azides afforded complexes with empirical formulae Zn(N3)2(pyNO)(H2O)2, Zn(N3)2(3picNO)2(H2O)2 and Cd(N3)2(3picNO)2(H2O) 2. The IR spectra of these complexes are measured and discussed. X-Ray single crystal diffraction showed for the first complex, which should be formulated as {[Zn(N3)2(H2O) 2](pyNO)}n, to consist of 1D chains of trans-[Zn(N 3)2(H2O)2]n, double end-on (μ-1,1) azido bridges and noncoordinated pyNO molecules. The other two complexes are isomorphous containing 1D trans-[M(N3) 2(H2O)2]n, double (μ-1,1) azido bridges, and hydrogen bonded noncoordinated 3picNO molecules. Each pyridine-N-oxide molecule forms three hydrogen bonds, whereas the 3-picoline-N-oxides form two hydrogen bonds. The metal centers exhibit distorted octahedral geometry.

Autor: Mautner, F.A., Gspan, C., Goher, M.A.S., Abu-Youssef, M.A.M.

Czasopismo: Monatshefte fur Chemie 134 (10), pp. 1311-1320 rok: 2003

Properties of complex of N-oxidized derivatives of pyridine with zinc chloride

Abstrakt

Permittivity, specific electric conductivity, and IR spectra of polycrystalline complexes of zinc dichloride with N-oxides of pyridine, isomeric picolines, and 2,6-lutidine of 1:2 composition were studied. It is shown that the enthalpy of an O...Zn bond is essentially dependent on electronic effects of methyl groups and the type of molecular packing in crystals. It is found that the complexes studied undergo a reversible avalanche-like ionization as the temperature rises from 18 to 40-70°C.

Autor: Ponomarenko, S.P., Dulnev, P.G., Borovikov, Yu.Ya., Sivachek, T.E., Makovetskij, V.P.

Czsopismo: Ukrainskij Khimicheskij Zhurnal 70 (3-4), pp. 34-39 Rok: 2004 język rosyjski

Physicochemical properties of complexes of zinc iodide with pyridine N-oxides

Abstrakt

Polycrystalline 1 : 2 complexes of ZnI2 with N-oxides of pyridine, picoline, and 2,6-lutidine were studied by IR spectroscopy, dielectrometry, and conductometry. An equilibrium between three solid phases was observed. These phases are characterized by different enthalpies of formation of intermolecular bonds and different mechanism of electronic effect transmission via these bonds. Gas-like thermal molecular motion in one of the phases of the 2,6-lutidine N-oxide complex was observed. Reversible chemical reactions on the surface of the crystalline 3-picoline N-oxide complex are initiated on exposure to an alternating electric field. Two complexes, similarly to the ZnCl2 complexes, are ionized in the cumulative mode on fast heating from 18-19 to 26-45°C. Partial activation energies of electrical conductivity of different ions were determined for a number of complexes and inorganic salts.

Autor: Ponomarenko, S.P., Dul'nev, P.G., Borovikov, Yu.Ya., Sivachek, T.E., Makovetskii, V.P.

Czasopismo: Russian Journal of General Chemistry 71 (11), pp. 1694-1700 Rok: 2001

Crystal structures of the cobalt(III), nickel(II), copper(II), and zinc(II) complexes of 2-thio-6-picoline N-oxide

Abstrakt

Structures of the following compounds have been solved: tris(2-thio-6-picoline N-oxide)cobalt(III), [Co(6MOS)3], orthorhombic, Pca21, a = 17.871(3), b = 14.061(2), c = 15.964(2) Å, V = 4011(1) Å3, Z = 8, and μ = 1.193 mm-1; bis (2-thio-6-picoline N-oxide)nickel(II), [Ni(6MOS)2], orthorhombic, Pbca, a = 15.602(8), b = 13.606(4), c = 13.348(8) Å, V = 2833(4) Å3 Z = 8, and μ = 1.655 mm-1; bis(2-thio-6-picoline N-oxide)copper(II), [Cu(6MOS)2], orthorhombic, Pbca, a = 13.914(5), b = 12.984(5), c = 15.663(6) Å, V = 2830(2) Å3, Z = 8, and μ = 1.836 mm-1; and bis(2-thio-6-picoline N-oxide)zinc(II), [Zn(6MOS)2], triclinic, P - 1, a = 7.9737(8), b = 11.7786(9), c = 7.9206(8) Å, α = 104.502(7), β = 104.495(8), γ = 93.445(8)°. V = 691.3(1) Å3 Z = 2, and μ, = 2.106 mm-1. The steric effect of the methyl group in the six-position of the N-oxide ring is considered in comparing these structures to complexes of 2-thiopyridine N-oxide.

Autor: West, D.X., Brown, C.A., Jasinski, J.P., Jasinski, J.M., Heathwaite, R.M., Fortier, D.G., Staples, R.J., Butcher, R.J.

Czasopismo: Journal of Chemical Crystallography 28 (12), pp. 853-860 Rok: 1998

Crystal structures of the picoline N-oxide complexes M(4-CH3C5H4NO)6(ClO 4)2 (M = Cu, Zn) and EPR spectra of the pure and zinc-doped copper complexes

Abstrakt

The hexakis(4-picoline N-oxide)copper and -zinc perchlorate complexes crystallize in the monoclinic system, space group P21/c, with the following unit cell dimensions: for the copper complex a = 9.523 (5) Å, b = 10.707 (8) Å, c = 20.512 (16) Å, and β = 92.47 (6)°; for the zinc complex, a = 9.467 (5) Å, b = 10.760 (5) Å, c = 20.531 (9) Å, and β = 92.46 (4)°. The structures were solved with the use of approximately 2400 independent reflections collected for each complex on a single-crystal diffractometer using Mo Kα radiation at ambient temperature. The final, conventional residuals were 0.097 and 0.082 for those reflections with I > 2σ(I), these rather high values being the result of the limited sizes of the data sets available for the structure determinations. While the complex cations in the two salts have only I symmetry, the coordination polyhedron in the zinc complex comes close to octahedral geometry with an average Zn-O distance of 2.114 Å. The coordination geometry for the copper complex, however, is in accord with the presence of a static Jahn-Teller distortion, the Cu-O distances being 1.965, 2.008, and 2.385 Å. Single-crystal EPR measurements, at both X- and Q-band frequencies, are also indicative of tetragonally elongated geometries for the copper-containing cation, both in the pure complex and in the case when it is doped into the zinc complex. The principal values of the g tensor average 2.32, 2.12, and 2.07. In the pure complex, the cations are oriented in approximately a ferrodistortive arrangement, and there is no evidence from the EPR spectra for any appreciable magnetic exchange between the two nonequivalent sites in the monoclinic cell. For the doped system, there is no evidence for the operation of a dynamic Jahn-Teller effect even though the zinc host complex is approximately octahedral. © 1981 American Chemical Society.

Autor: Wood, J.S., Day, R.O., Keijzers, C.P., De Boer, E., Yildirim, A.E., Klaassen, A.A.K.

Czasopismo: Inorganic Chemistry 20 (7), pp. 1982-1987 Rok:1981

Electrical and spectral properties of manganese dichloride complexes with N-Oxides of pyridine derivatives

Abstrakt

Polycrystalline complexes of MnCl2 with N-oxides of pyridine, 2-picoline, and 2,6-lutidine contain a molecule of strongly retained crystallization water; two types of the labile networks of hydrogen bonds are formed on the crystal surface. Under solar radiation the long-lived F-centers are formed in the crystals, imparting a specific color to the compounds. The thermal motion of MnCl2 complexes with lutidine N-oxide in the unit cells can be described as gas-like motion. At low temperatures the electrical conductivity is predominantly maintained by protons, whereas at high temperatures another mechanism of conductivity arises.

Autor: Borovikov, Yu.Ya., Dul'nev, P.G., Ponomarenko, S.P., Sivachek, T.E.

Czasopismo: Russian Journal of General Chemistry 71 (5), pp. 789-794 Rok: 2001