Mapping Out the Molecular Interplay in Monohalobenzene Inclusion complexes of p-H-calix[5]arene Using Hirshfeld Surfaces

Solid-state inclusion complexes of p-H-calix[5]arene with fluoro-, chloro-, bromo-, and iodobenzene have been structurally authenticated using X-ray diffraction data with a detailed analysis of the Hirshfeld surfaces facilitating an understanding of the type and nature of intermolecular interactions in the supermolecules and extended structures. All but the iodobenzene complexes are isostructural forming columnar arrays involving three crystallographicatly related 1:1 host-guestsupermolecules (halobenzenencalix[5]arene); three halobenzene molecules from different supermolecules are associated via C-H... X interactions for hydrogen atoms ortho to the halogen atoms, effectively creating a larger cavity from close proximity of three calix[5]arenes. The iodobenzene inclusion complex has sheets of calixarenes rather than columns in the extended packing, presumably due to the increased size of iodine circumventing the formation of the aforementioned interplay of three halobenzene molecules.