Tetraallyl Ethers of Thiacalix[4]arenes in the 1,3-Alternate Conformation

The O-alkylation of thiacalix[4]arene and of two derivatives substituted in p-position by NO2 and p-N=N-C6H4-NO2 with allylbromide leads to tetraallyl ethers in the 1,3-alternate conformation (1-3) as proved by X-ray crystallography. Compound 1 crystallized in the trigonal space group P3(2)21 with unit cell parameters a = 10.9608(4) angstrom, b = 10.9608(4) angstrom, c = 24.6730(12) angstrom; alpha = 90 degrees, beta = 90 degrees, gamma = 120 degrees and Z = 3. Compound 2 crystallized in the orthorhombic space group Pbca with unit cell parameters a = 12.8608(4) angstrom, b = 17.5209(5) angstrom, c = 33.6527(9) angstrom; alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees and Z = 8. Compound 3 crystallized in the monoclinic space group P2(1)/n with unit cell parameters a = 18.7825(19) angstrom, b = 17.6662(13) angstrom, c = 19.7828(18) angstrom; alpha = 90 degrees, beta = 114.152(7)degrees, gamma = 90 degrees and Z = 4. Subtle differences in the molecular shape of the calix[4]arene core were found. The unsubstituted compound 1 forms three alternating layers with parallel tubes of different orientation, while for 3 all molecules are arranged in tubes parallel to the a-axis. Layers of molecules parallel to the a, b-plane are found for compound 2.