Abstract
Supramolecular assemblies of (±)‐2,2′‐dihydroxy‐1,1′‐binaphthyl (BINOL, A), with aza donor molecules including 2,2′‐bipyridine (B) and naphthodiazine (C), have been synthesized and characterized by single‐crystal X‐ray diffraction methods. Two inclusion complexes crystallize in the triclinic system with P‐1 space group. In the inclusion complex between A and B, two molecules of A and two molecules of B are linked each other by intermolecular hydrogen bonds with two molecules of water as the bridges, forming a centrosymmetric dimer with formula of A~2~(H~2~O)~2~B~2~; while in the inclusion complex between A and C, the molecule C virtually acts as a bridge to link molecules A through intermolecular OH…︁N hydrogen bonds, forming a short‐chain supramolecular block with a formula of A~2~'C~3~ Besides the hydrogen bonding interaction between the host and guest molecules, π‐π stacking interactions also play an important role in the solid‐state packing of these two inclusion complexes. The structural information disclosed on the complex between dihydroxy compound and aza hydrogen bond acceptors in this work would be particularly important for the rational design of supramolecular organic functional materials.