Three related benzoannelated diazapolyether macrocycles: effects of macrocycle ring size and position of benzo groups on hydrogen bonding of the amine H atoms

The benzoannelated diazapolyether macrocycles 6,7,9,10,17,18‐hexahydro‐5H,11H‐8,16,19‐trioxa‐5,11‐diazadibenzoa,g]cyclopentadecene, C₁₈H₂₂N₂O₃, (I), 6,7,9,10,12,13,20,21‐octahydro‐5H,14H‐8,11,19,22‐tetraoxa‐5,14‐diazadibenzoa,g]cyclooctadecene, C₂₀H₂₆N₂O₄, (II), and 6,7,9,10,17,18,20,21‐octahydro‐16H,22H‐5,8,11,19‐tetraoxa‐16,22‐diazadibenzoa,j]cyclooctadecene 0.3‐hydrate, C₂₀H₂₆N₂O₄·0.304H₂O, (III), show different patterns of hydrogen bonding. In (I), the amine H atoms participate only in intramolecular hydrogen bonds with ether O atoms. In (II), the amine H atoms form intramolecular hydrogen bonds with the phenoxy ether O atoms and intermolecular hydrogen bonds with alkyl ether O atoms in an adjacent molecule, forming a chain linking the macrocycles together via an R₂²(10) motif. Molecules of (II) were found on a crystallographic twofold axis. In (III), the amine H atoms participate in a hydrogen‐bond network with adjacent ether O atoms and with a water molecule having a partial occupancy of 0.304 (6)] that links the molecules together via a C₂²(7) motif.