Noncovalent interactions between classical supramolecular synthons in solution: Hydrogen bonding in hindered 2-acylaminopyridine/2-pyridone associates

► Two classical supramolecular synthons form associates in solution. ► Steric effects of substituents present in both counterparts drive association. ► DFT calculations predict the properties of hydrogen bonds explaining observations. ► Compounds with bulky groups do not dimerize but form heteroassociates.