A squaramido-based model compound with the ability to establish an intramolecular hydrogen bond has been designed to study the effect of preorganization on its polymorphism and the cocrystallization with resorcinol. Three out of the four expected supramolecular synthons have been observed in two polymorphs and two cocrystals with resorcinol, whose crystal structures have been solved from X-ray diffraction laboratory data using direct-space strategies.