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-diaza­dibenzo­[a,g]­cyclo­penta­decene, C₁₈H₂₂N₂O₃, (I), 6,7,9,10,12,13,20,21-octa­hydro-5H,14H-8,11,19,22-tetra­oxa-5,14-diaza­dibenzo­[a,g]­cyclo­octa­decene, C₂₀H₂₆N₂O₄, (II), and 6,7,9,10,17,18,20,21-octa­hydro-16H,22H-5,8,11,19-tetra­oxa-16,22-diaza­dibenzo­[a,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.