The cubic structure of the cubane molecule, C8H8, gives rise to many u
nusual properties in the solid stale. X-ray powder diffraction measure
ments of solid cubane reveal a large thermal expansion. followed by a
strong first-order phase transition at 394 K from an orientationally o
rdered phase (<R(3)over bar>) to a noncubic orientationally disordered
phase (<R(3)over bar> or R3m). The resulting volume expansion is 5.4%
. Model calculations predict the correct low- and high-temperature pha
ses. The orientational potential in the disordered phase resembles a r
ounded square well over a large angular range. Cubane thus represents
an ideal example of a system with large-amplitude collective motions.