Cyclohexane plastic phase I: single-crystal diffraction images and new structural model

Abstract

The plastic phase of cyclohexane (polymorph I) was studied by Kahn and co-workers, without achieving a satisfactory determination of the atomic coordinates [Kahn et al. (1973). Acta Cryst. B29, 131–138]. The positions of the C atoms cannot be determined directly as a consequence of the disorder in a high-symmetry space group, an inherent feature of plastic materials. Given this situation, the building of a polyhedron describing the disorder was the main tool for determining the molecular structure in the present work. Based on the shape of reflections {111}, {200} and {113} in space group Fm 3 m, we assumed that cyclohexane is disordered through the action of rotation group 432. The polyhedral cluster of disordered molecules is then a rhombic dodecahedron centred on the nodes of an fcc Bravais lattice. The vertices of this polyhedron are the positions of C atoms for the cyclohexane molecule, which is disordered over 24 positions. With such a model, the asymmetric unit is reduced to two C atoms placed on special positions, and an acceptable fit between the observed and calculated structure factors is obtained.