An isomer grid of nine fluoro-N-(pyridyl)benzamides (Fxx) (x = para-/meta-/ortho-) has been examined to correlate structural relationships between the experimental crystal structure and ab initio calculations, based on the effect of fluorine (Fx) and pyridine N-atom (x) substitution patterns on molecular conformation. Eight isomers form N—H...N hydrogen bonds, and only one (Fom) aggregates via intermolecular N—H...O=C interactions exclusively. The Fpm and Fom isomers both crystallize as two polymorphs with Fpm_O (N—H...O=C chains, P-syn) and Fpm_N (N— H...N chains, P-anti) both in P21/n (Z0 = 1) differing by their meta-N atom locations (P-syn, P-anti; Npyridine referenced to N—H), whereas the disordered Fom_O is mostly P-syn (Z` = 6) compared with Fom_F (P-anti) (Z` = 1). In the Fxo triad twisted dimers form cyclic R22(8) rings via N—H...N interactions. Computational modelling and conformational preferences of the isomer grid demonstrate that the solid-state conformations generally conform with the most stable calculated conformations except for the Fxm triad, while calculations of the Fox triad predict the intramolecular N— H...F interaction established by spectroscopic and crystallographic data. Comparisons of Fxx with related isomer grids reveal a high degree of similarity in solid-state aggregation and physicochemical properties, while correlation of the melting point behaviour indicates the significance of the substituent position on melting point behaviour rather than the nature of the substituent.