Abstract
Monoclinic (N2H6)3Zr2F13·F crystallizes in space group P21-C 22 (No. 4) with unit cell dimensionsa=5.670(1),b=10.984(2),c=10.601(2) Å,β=93.88(1)°,V=658.7(4) Å3 andZ=2. Two different types of N2H6 2+ ions are present. One is involved in strong H-bonds to F− ions in infinite chains running along the a axis (the shortest N-F distance is 2.437(5) Å), and the other links the structure through weaker bi- and trifurcated H-bonds to fluorine ligands of the Zr2F13 5− ions. The N-N bond lengths range from 1.430(5) to 1.446(5) Å with apparently no meaningful correlation to the type of N2H2 2+ ions. The Zr2F13 5− ions have very nearly C2 point symmetry and are formed by joining two distorted bicapped trigonal prisms of ZrF8-units through a common face. Distances of Zr-F terminal bonds range from 2.015(2) to 2.112(2) Å and of bridging bonds from 2.133(2) to 2.212(2) Å. (N2H6)3Hf2F13·F is isomorphous. The vibrational spectra of the two compounds are nearly identical, with the exception of a strong infrared band, which is assigned to a stretching mode with the moving central atom within the anion. The anion part of the spectrum is simple, showing broad unresolved bands. The cation part shows two types of N2H6 – ions. H-Bonding is strongly present in the spectra, but no simple correlations with the H-bond strength is evident.
Similar content being viewed by others
References
Cameron, T. S., Knop, O., and Macdonald, L. A. (1983)Can. J. Chem. 61, 184.
Clark, R. J. H., Bradley, D. C., and Thornton, P. (1972)The Chemistry of Titanium, Zirconium and Hafnium, Pergamon Texts in Inorganic Chemistry, Vol. 19 (Pergamon Press, Oxford), p. 440–448).
Dean, P. A. W., and Evans, D. F. (1967)J. Chem. Soc. 698.
Gantar, D., Rahten, A. (1986)J. Fluorine Chem. 34, 63.
Gantar, D., Rahten, A., and Volavšek, B. (1988)J. Fluorine Chem. 41, 335.
Golič, L., Kaučič, V., and Kojić-Prodić, B. (1980)Acta Crystallogr. B 36, 659.
Hadži, D. (1972)Chimia 26, 7.
Herak, R. M., Malčič, S. S., and Manojlović, Lj. (1965)Acta Crystallogr. 18, 520.
Herschbach, D. R., and Laurie, V. W. (1961)J. Chem. Phys. 35, 458.
Joesten, M. D., and Schaad, L. J. (1974)Hydrogen Bonding (Marcell Dekker, Inc., New York).
Kojić-Prodić, B., Matković, B., and Šćavnićar, S. (1971a)Acta Crystallogr. B 27, 635.
Kojić-Prodić, B., Sćavničar, S., and Matkovič, B. (1971b)Acta Crystallogr. B 27, 638.
Kronberg, M. L., and Harker, D. (1942)J. Chem. Phys. 10, 309.
Lane, A. P., and Sharp, D. W. A. (1969)J. Chem. Soc. (A), 2942.
Leban, I., Arhar, A., Jordanovska, V., and Golič, L. (1988)Acta Crystallogr. C 44, 372.
Milićev, S., and Maček, J. (1984)J. Chem. Soc. Dalton Trans. 297.
Milićev, S., and Maček, J. (1985)Spectrochim, Acta 41A, 651.
Rahten, A., and Milićev, S. (1990) In press.
Slivnik, J., Šmalc, A., Sedej, B., and Vilhar, M. (1964)Vestn. Slov. Kem. Drus. 11, 53.
Slivnik, J., Jerković, B., and Sedej, B. (1966)Monatsh. Chem. 97, 820.
Smith, P. W., Stoessiger, R., and Turnbull, A. G. (1968)J. Chem. Soc. (A), 3013.
Snyder, R. G., and Decius, J. C. (1959)Spectrochim. Acta 13, 280.
Toth, L. M., and Bates, J. B. (1974)Spectrochim. Acta 30A, 1095.
Velsko, S. P. (1986)Proc. Soc. Photo-Opt. Instrum. Eng. 681, 25.
Wells, A. F. (1986)Structural Inorganic Chemistry (Clarendon Press, Oxford), fifth edition, pp. 471–474.
Zalkin, A., Eimerl, D., and Velsko, S. P. (1988)Acta Crystallogr. C 44, 2050.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Rahten, A., Leban, I., Milićev, S. et al. Crystal structure and vibrational spectra of hydrazinium (2+) tri-μ-fluoro bis[pentafluorozirconate (IV)] fluoride and vibrational spectra of its hafnium analogue. Journal of Crystallographic and Spectroscopic Research 20, 9–15 (1990). https://doi.org/10.1007/BF01181669
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF01181669