Symmetry lowering in crystalline solid solutions: a study of cinnamamide–thienylacrylamide by X-ray and neutron diffraction and solid-state photochemistry

Abstract

Principles are outlined for symmetry lowering of a mixed crystal composed of host and tailor-made additive molecules, based on selective occlusion of the latter through a subset of surface sites of the growing crystal, the symmetry of the surface generally being lower than that of the bulk. A survey is given of the various methods and approaches used to detect the reduction in symmetry. These include changes in crystal morphology, detection of enantiomeric segregation of chiral additives in ‘centrosymmetric’ crystals, generation of second-harmonic optical signals, optical birefringence, asymmetric photoreactions in the crystalline state and X-ray and neutron diffraction. The last two methods are applied to mixed crystals of cinnamamide (host) and thienylacrylamide (additive). The diffraction analysis demonstrated that the mixed crystals are composed of six sectors of reduced symmetry, from monoclinic centrosymmetric P21/c to triclinic P1 in four sectors and possibly Pc in the remaining two. The X-ray diffraction data were not sufficiently accurate to permit assignment of the absolute structures of the P1 sectors with the use of anomalous X-ray scattering. Thus, by this method one could not ascertain the absolute orientation of the guest molecules on the surface sites through which they were selectively occluded. This ambiguity was resolved by assignment of the absolute configuration of the chiral heterophotodimers, between host and guest, in enantiomeric excess in the P1 sectors, after irradiation with UV light. These results led to the definite conclusion that the selective occlusion of thienylacrylamide arises from a replacement of attractive C–H⋯π(electron) interactions between host molecules by repulsive sulfur (lone-pair electron)⋯π(electron) interactions between guest and host at the crystal surfaces.