Abstract
The results of a low-temperature spectroscopic investigation of crystals of the highest hydrate of perchloric acid have been presented. A brief review of the literature data on the problem of the structure of crystals of HClO4·5.5H2O (I) has been given. It follows from the review that the negative results obtained by Mootz et al. [J. Am. Chem. Soc., Vol. 109, No. 4, 1200 (1987)] when they refined a clathrate test model of the cubic structure of I is attributable to the mesomorphic structure of the crystals, which is characteristic of a plastic phase. The results of an analysis of the IR and Raman spectra of the optically anisotropic α plastic phase of I and the isotropic β plastic phase have made it possible to specify some details of the clathrate model. The vibrational spectra of deuterated and undeuterated solid solutions of I with components of the acid-water system have been interpreted in the framework of the improved clathrate model. Laws governing the structure of the labile polyhedrons in the water-cation host structure and the formation of the anion sublattice, which is insensitive to variation of the composition, have been revealed for the two phases of variable composition α-HClO4·nH2O (n=5.4 to 5.6 at −180°C) and β-HClO4·nH2O (n=5.2 to 6.0 at −180°C).
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Additional information
Institute of New Chemical Problems, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 2, pp. 51–61, March–April, 1991.
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Karelin, A.I. Solid solutions, clathrate structures, and vibrational spectra of plastic crystals of HClO4·5.5H2O. J Struct Chem 32, 199–208 (1991). https://doi.org/10.1007/BF00777188
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DOI: https://doi.org/10.1007/BF00777188