Five representatives of 4,5-diaryl-substitted 3-hydroxy-2,2′-bipyridine-6-carbonitriles were studied by single-crystal X-ray diffraction. The specific features of the molecular structures of these compounds and the effect of substituents on the crystal packing are discussed. The results of this study may be of interest in terms of the possible biological activity of this series of compounds and their use as polydentate N,N- or N,O-type ligands. © 2023, Springer Science+Business Media LLC.