On the Polymorphism of White Phosphorus

White phosphorus occurs in three modifications. The α form, which exists at roomtemperature, transforms reversibly to the β form at –77°C. The α · β transformation may be strongly delayed. Quenching the α form to –185°C followed by slow warming results in an exothermic reactions with formation of the γ form which transforms into the β form at –120°C in an endothermic reaction. A transition β · γ is not observed. The γ form is characterized by its powder diagram. The structure of the β form is redetermined from a single crystal at –185°C (P., α = 547.88(5), b = 1078.62(11), c = 1096.16(11)pm, α= 94.285(8), β = 99.695(7), γ = 100.680(7)., V = 623.79(10) · 106 pm3, Z = 6 formula units per cell). The P4 molecules exhibit pronounced librational motion in spite of the low temperature of investigation. The arrangement of the centers of the tetrahedra corresponds to the atom positions in the γ‐plutonium structure, which is discussed in relation to the bcc structure.