Effect of remote substituents on solid state packing interactions in macrocyclic crownophanes derived from 1,3,5-triaroylbenzenes

A series of four structurally related crownophanes has been prepared and characterized by X-ray crystallography. The crownophanes are based upon a 1,3,5-triaroylbenzene framework and were synthesized via enaminone/alkyne cyclotrimerization. The crownophanes differ in the identity of a peripheral substituent attached to a remote arene ring that is not part of the cyclophane macrocycle. Solid state structural characterization reveals that crownophanes with remote phenyl and phenol substituents self-assemble to form centrosymmetric dimers. Incorporation of remote alkoxy groups (methoxy or ethoxy) disrupts dimerization and leads to catameric networks. Each crownophane crystallized as an inclusion complex or a hydrate and, in one instance, water was found to occupy the macrocyclic cavity.