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Metal-Oxygen Vibrations

  • Chapter
Low-Frequency Vibrations of Inorganic and Coordination Compounds

Abstract

There are several types of water in inorganic salts. Those water molecules that are coordinated to the metal and retain their identity in solution —e.g., aquo-ions of the type [M(H2O)a]b—are termed coordinated water, and those water molecules that are hydrogen bonded to other water molecules or to the anion or to both are termed lattice water. The distinction, however, is not clear-cut, for some coordinated water may also engage in hydrogen bonds within the crystal. Confirmation of structures of this type has come from neutron diffraction studies of hydrates. Studies by Taylor et al. 1 with Th(NO3)4·5H2O showed coordinated water,1 water-water hydrogen bonds, and water hydrogen bonded to the nitrate. Figure 5–1 illustrates the structure of Th(NO3)4·5H2O. Uranyl nitrate hexahydrate exhibits similar types of environments for the water molecules.2 Stable solids containing the oxonium ion (H3O+) have also been reported.3–7 Recently, single-crystal neutron diffraction evidence for the diaquohydrogen ion in trans-[Co(en)2Cl2]+Cl-(H5O2)+Cl- has been found.8 The hydrogen bonding in the diaquohydrogen ion (trans.) is illustrated in Fig. 5–2. Complex structures of the aforementioned types (as illustrated by Th(NO3)4 · 5H2O and [Co(en)2Cl2]+Cl-(H5O2)+Cl-) should be considered to be typical of hydrates rather than exceptional.

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    John R. Ferraro

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Ferraro, J.R. (1971). Metal-Oxygen Vibrations. In: Low-Frequency Vibrations of Inorganic and Coordination Compounds. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-1809-5_5

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