Crystalline hydrates of pentafluoridozirconic acid HZrF5∙3H2O, HZrF5∙2H2O and intermediate product of the thermal decomposition of acids ZrF4∙H2O were studied by vibrational spectroscopy and thermogravimetry. It is shown that the crystalline hydrates HZrF5∙nH2O (n=2, 3) are salts with complex H5O2+ and H7O3+ cations. Based on the results of quantum chemical calculations, the bands in the IR and Raman spectra were assigned.
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