Bi-layer complexes incorporating large organic cations and anionic tetra-p-sulfonated calix[4]arene capsules

H(4)TMTAA(2+)/18-crown-6, H(4)TMTAA(2+)/2-hydroxybenzimidazole and cyclamH( 4) (4+) self-assemble with sodium tetra-p-sulfonated calix[4]arene to form capsules within overall bilayer structures. [H(4)TMTAA (2+)](2)[trans-{Na()subset of (18-crown-6)(H2O)(2)}subset of [(p-O3S-calix[4]arene)(2)] + 3H()]. 17H(2)O crystallises in the triclinic space group P1 and contains the " Russian Doll" assembled superanion capsule, [Na(+)subset of (18-crown-6)(OH 2) (2)}subset of{(p-O3S-calix[4]arene)(2))(7-). [H(4)TNlTAA(2+)](2)[(C7N2CH 7+)(2)subset of [(p-O3S-calix[4]arene)(2)} + 2H(+)]. 17H(2)O also crystalli ses in the triclinic space group P1 and also contains a superanion capsule with two 2-hydroxybenzirnidazolium cations as the capsule core, [cyclamH(4) (4+)][{cyclamH(4) (4+)}subset of {(p-O3S-calix[4]arene)(2)}]. 18H(2)O cryst allises in the space group P2(1)/n and is an example of a slipped capsule, with the slight "mismatch" allowing stronger internal capsule H-bonding. Th e cations influence the spacing between the bilayers and can span the calix arene layers.