Organic clays. Synthesis and structure of Na5[calix[4] arene sulfonate] · 12 H2O,K5[calix[4]arene sulfonate]·8 H2O,Rb5[calix[4]arene sulfonate]·5 H2O,and Cs5[calix[4] arene sulfonate] ·4 H2O

The title calixarenes all exist in the solid state as bilayers of anionic calixarenes in the cone configuration. These layers alternate with inorganic regions which contain the cations and the water molecules. The overall structures bear a close resemblance to those found for clay minerals. The sodium salt crystallizes in the triclinic space groupP witha = 10.998(6),b = 13.582(5),c = 14.472(5) Å, = 74.01(3), = 89.09(4), = 86.50(4)°, andZ = 2 forD _calc = 1.72 g cm^–3. Refinement based on 4727 observed reflections led to a conventionalR = 0.050. The potassium salt crystallizes in the triclinic space groupP witha = 11.815(9),b = 13.636(6),c = 14.040(9) Å, = 100.24(5), = 111.86(9), = 95,14(9)°, andZ = 2 forD _calc = 1.77 g cm^–3. Refinement based on 2977 observed reflections led toR = 0.15. The rubidium and cesium salts are isostructural and crystallize in the monoclinic space groupP2₁/n with parameters for RbCs]a = 11.603(5) 11.704(3)],b = 28.607(8) 29.747(9)],c = 12.512(5) 12.604(4)] Å, = 91.70(4) 91.63(2)°], andZ = 4 forD _calc = 2.01 2.24] g cm^–3. Refinement based on 1750 4257] observed reflections led toR = 0.108 0.075]. Disorder of the cations was observed for the rubidium and cesium salts. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82074 (95 pages).