3,6,9,16,19,22-Hexaazatricyclo

The adduct (1) formed between the hexaaza macrocycle 3,6,9,16,19,22-hexaazatricyclo[22.2.2.2(11,14]triconta-1(26),11(29),12,14(30),24,27-hexaene, C24H38N6, and 4,4'-sulfonyldiphenol, O2S(C6H4OH)2, is a salt [(C24H40N6)2+].2[(HOC6H4SO2C6H4O)-], and the adduct (2) formed by the same macrocyclic amine with 4,4'-biphenol is an aquated salt which also contains neutral biphenol molecules, [(C24H40N6)2+]. 2[(HOC6H4C6H4O)-].(HOC6H4C6H4OH).2H2O. In both compounds the cations lie across centres of inversion: there are two crystallographically distinct cation sites in (1) and the conformations of the cations occupying them are quite different. In (2) the single type of cation site is occupied by a conformationally disordered cation: the major and minor components represent two further distinct conformers. In (1) the anions are linked by O-H...O hydrogen bonds into chains, and each cation is linked by a total of six N-H...O hydrogen bonds to anions in four different chains, so linking the chains into continuous sheets. In (2) the anions and the water molecules are linked into sheets, which are further linked into a continuous three-dimensional framework by both the cations and the neutral biphenol units.