Macrocyclic compounds are a versatile group of ligands that can be used for selective complexation of cationic, anionic, and neutral chemical species. Macrocyclic compounds containing an acylhydrazone functional group can be prepared by the reaction of polyhydrazine and polyaldehyde precursors. To investigate the structural features of acylhydrazone macrocycles, we have prepared and crystallized two novel macrocyclic compounds (achyM5 and achyM6). The prepared compounds are ring analogs containing 22 (achyM5) and 23 (achyM6) atoms in the inner macrocyclic ring. Both compounds are N₅O₄-donor macrocycles composed of pyridine and dibenzaldehyde moieties connected by acylhydrazone groups. Although rather similar, the compounds differ in the subtle geometrical parameters such as dihedral angles, puckering amplitude, and inner macrocyclic hole size. These parameters show that the larger macrocycle (achyM6) is more deformed (puckering amplitude of 2.721(3)). In the crystal structure of achyM5, the adjacent macrocycles are connected via N-H∙∙∙O hydrogen bonds between NH groups and carbonyl oxygen along the a-axis. Interestingly, there is a short contact between the imine and pyridine N atoms (3.045 Å) of adjacent macrocycles that can be regarded as a weak N∙∙∙N pnictogen bond. The final 3D arrangement is achieved via weak C-H∙∙∙C and π∙∙∙π interactions. The achyM6 crystallizes as a water solvate, with two symmetry-independent molecules in the asymmetric unit. The water molecule is located approximately in the center of the macrocyclic ring and connected via N-H∙∙∙O hydrogen bonds. In the crystal, the adjacent macrocyclic molecules are primarily connected through O-H∙∙∙O hydrogen bonds that involve a water molecule and carbonyl oxygen, and N-H∙∙∙O hydrogen bonds between NH groups and carbonyl oxygen. A short N∙∙∙N contact between the imine and pyridine N atoms (3.007 Å) of adjacent macrocycles is also present, implying the importance of these interactions in the overall crystal stability of these systems.