Abstract

Molecular structures of P4O6 and As4O6 were determined from electron diffraction data. P4O6 was found to have the symmetry of the point group Td with an angle P–O–P of 128.5±1.5°, and a P–O distance of 1.67±0.03A. In this structure the phosphorus oxygen distances and the phosphorus valence angles were preserved with resulting deformation of the oxygen valence angle. The separation of the arsenic atoms in As4O6 was found to be 3.20±0.05A. Because of the predominant scattering of the arsenic atoms it was difficult to determine the oxygen valence angle, As–O–As. Values of 120°, 127.5° and 140° gave approximate agreement between the observed and calculated positions of maxima. Electron diffraction photographs obtained from P4O10 differ considerably from those found for P4O6. It was not possible to explain all of the features of the P4O10 diffraction pattern by a model having the symmetry of the point group Td and it is thought that the structure might be one of lower symmetry. Data were obtained on P4O8 which indicated that it has approximately the same electron diffraction pattern as P4O10.

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