The polymorphs of (Z)-2-fluoro-N′-phenyl benzamidamide with multiple Z′ produce quasi-isostructural supramolecular architectures, wherein C–H⋯F interaction plays a significant role. The energy framework analysis indicates 2D structural similarities in the interaction topologies of these crystalline forms. The results point to a unique class of ‘quasi-isostructural polymorphs’ which are nearly equi-energetic crystal structures exhibiting high degrees of similarity in physical properties.