Intermolecular hydrogen bonds between 2,6-bis(acylamino)pyridines and dipyridin-2-ylamine as well as 4,4-dimethylpiperidine-2,6-dione are responsible for relatively strong interactions between these species. Association has been found to be significantly affected by the size of acyl substituent (chemical shift of the NH proton was used as the main probe in determination of the association constants). Calculations at the DFT level of theory are in line with the experimentally observed results. Calculated energies of the interactions between the complex congeners also show the size of the substituent to affect the association. Conformational changes in the dipyridin-2-ylamine molecule are shown to adapt a geometry suitable for formation of efficient hydrogen bonding.