The solid-state packing of a two-component mixture consisting of the alpha,alpha,alpha,alpha steroisomer of a calix[4]pyrrole resorcinarene hybrid and tetramethylammonium chloride is controlled by the relative stoichiometry of the mixture in solution. The use of a high molar excess of the ammonium salt induces, in the solid state, a self-assembly process of the calix[4]pyrrole into a supramolecular hexameric structure that corresponds to an octahedron.