Structure-property correlations in bending and brittle organic crystals

Abstract

Bending of crystals of molecular solids occurs when the strength of intermolecular interactions in orthogonal directions is significantly different. We report here a survey of 60 molecular crystals and establish a causative correlation between bending and crystal packing. This group contains crystals with 4 and 8 Å crystal axes and includes 1D, 2D, 3D, isostructural, polymorphic, stacked, interlocked, single, and multicomponent crystals and solvates. We found that 17 of these 60 crystals may be bent, whereas the rest are brittle and cannot be bent plastically. The bending crystals could be deformed into many shapes; sometimes, they could even be flattened upon themselves without breakage. A model for bending is proposed using the information obtained from X-ray diffraction, face indexing, and mechanical property measurements on both bending and non-bending (brittle) crystals. The bending and brittleness of these molecular crystals are discussed in comparison with the deformation behavior of metals. Molecular crystals show practically no change in volume and the lengths of the inner and the outer arcs and the sample thickness are unchanged following plastic bending. This is in contrast with the bending of metallic materials, in which a decrease in thickness is evident. Isotropic crystals with comparable intermolecular interactions in the three orthogonal directions are "cross-linked"and do not bend; they are hard and brittle. Mechanical properties of molecular crystals are important because they vary with the crystal form and have major implications for large-scale processing and handling of materials in industry, especially the pharmaceutical industry.