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C. R. Acad. Sci. Paris 260, 4764–4767 (1965) 2. C. Cros, Le syste`me silicium-sodium. The`se de Troisie`me Cycle, Universite´ de Bordeaux (1965) 3. S. Kasper, P. Hagenmuller, M. Pouchard, C. Cros, Clathrate structures of silicon. Science 150, 1713–1714 (1965) 4. C. Cros, Sur quelques nouveaux siliciures et germaniures alcalins a` structure clathrate: e´tude cristallographique et physique. The`se Universite´ de Bordeaux (1970) 5. C. Cros, M. Pouchard, Sur les phases de type clathrate du silicium et des e´le´ments apparente´s (C, Si, Ge, Sn): une approche historique.
In the clathrate-I crystal structure with ideal composition X8(H2O)46 (X stands for a small molecule), the framework is built of water molecules connected via hydrogen bonds (Fig. 2, left). The covalent- and hydrogen-bonded O–H–O groups are arranged in such a way that pentagondodecahedral and tetrakaidecahedral cages are formed. The whole network can be described as being formed by neutral [OH4/2] groups. It is therefore uncharged and the cavities can bear neutral molecules of appropriate size according to the balance (X0)8[(OH4/2)0]46 = X8(H2O)46.
The interatomic distances are usually close to the sum of the covalent radii of the constituting atoms. g. 42 Å for Cs8-xSi46 [37]. e. it is a crossing point of six pentagonal faces. All bond angles here are close to the tetrahedral one. Position 3 is located at the crossing point of five pentagonal and one hexagonal face, having one angle within the hexagon which tends to be much larger than the tetrahedral one. Position 1 is located at the crossing point of two perpendicular six-ring faces and four five-ring faces of adjacent tetrakaidecahedrons.
Physik III Vorlesung by Hebbeker.
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