CRYSTAL-STRUCTURE AND BONDING OF ORDERED C60

STRUCTURAL studies 1-3 of crystalline C60 (ref. 4) have indicated that at room temperature the C60 molecules are orientationally disordered and the crystal structure may be regarded as a face-centred cubic configuration of C60 spheres. Below 249 K, however, the molecules become orientationally ordered 3 and a simple cubic lattice results, corresponding to a symmetry change from Fm3BAR to Pa3BAR. Here we present the results of a neutron powder diffraction study of the low-temperature ordered structure, which reveals the packing configuration of the C60 molecules. The C60 units are rotated in an anticlockwise manner around the [111] direction by approximately 98-degrees from the ideal Fm3BAR configuration. This apparently arbitrary rotation in fact results from an optimized ordering scheme in which electron-rich short (1.391-angstrom) inter-pentagon bonds face the electron-poor pentagon centres of adjacent C60 units. The high symmetry of the C60 molecule allows these interactions to be optimized identically for all twelve nearest neighbours, a possibility that is by no means intuitively obvious. The bonds common to a given pentagon are somewhat longer (1.455 angstrom). The high degree of bonding optimization and the absence of bonding frustration accounts for the high ordering temperature of 249 K (ref. 5).