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

Abstract

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 group Pī with a = 10.998(6), b = 13.582(5), c = 14.472(5) A, α= 74.01(3), β = 89.09(4), γ = 86.50(4)°, and Z = 2 for D calc = 1.72 g cm−3. Refinement based on 4727 observed reflections led to a conventional R = 0.050. The potassium salt crystallizes in the triclinic space group Pī with a = 11.815(9), b = 13.636(6), c = 14.040(9) A, α = 100.24(5), β = 111.86(9), γ = 95.14(9)°, and Z = 2 for D ca1c = 1.77 g cm−3. Refinement based on 2977 observed reflections led to R = 0.15. The rubidium and cesium salts are isostructural and crystallize in the monoclinic space group P21/n with parameters for Rb[Cs] a = 11.603(5) [11.704(3)], b = 28.607(8) [29.747(9)], c = 12.512(5) [12.604(4)] A, β = 91.70(4) [91.63(2) °], and Z = 4 for Dcalc = 2.01 [2.24] g cm−3. Refinement based on 1750 [4257] observed reflections led to R = 0.108 [0.075]. Disorder of the cations was observed for the rubidium and cesium salts.