Topologies of ladder packing arrangements in crystal structures of five azaheterocyclic phosphonates were characterized by four geometrical descriptors introduced in the paper. The structural analysis was augmented by detailed calculations on interactions stabilizing the molecular assemblies. Intermolecular energies were evaluated using PIXEL and DFT(M062x-GD3) methods. Additionally, fingerprint plots derived from the Hirshfeld surfaces were generated for each structure to characterize the crystal packing arrangement in detail. All structures are stabilized by the relatively weak hydrogen bonds and nonbonding interactions involving aromatic rings, i.e., π···π, C–H···π, and (lp)···π effects. Distribution of the molecular electrostatic potential demonstrates that positively charged, endocyclic sulfur atoms are prone to chalcogen–chalcogen (S···O) bonding. Analysis of the supramolecular motifs shows the lack of a common synthon responsible for the ladder packing arrangements. However, the striking geometry similarity of all molecules indicates that ladder packing is based on a shape oriented molecular recognition and mostly driven by the van der Waals forces. The intermolecular electrostatic effects are crucial for stabilizing and fixing geometry of the already formed molecular clusters.