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The crystal structure of two new cubic phases in the silicon-sodium system have been solved from their x-ray diffraction patterns. Both structures are of the clathrate type found for gas hydrates, consisting of tetrahedral networks which are combinations of pentagonal dodecahedra with 14-face polyhedra in one case and with 16-face polyhedra in the other case. There is strict correspondence between the silicon positions and the oxygen positions of the hydrate structures. For one compound, Na(8)Si(46), the centers of all polyhedra are occupied by sodium atoms. For the other compound, there occurs only partial occupancy of the polyhedral cages.

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