The structures of three syn-1,3-dialkoxythiacalix[4]arenes with unusual conformations in the solid state are reported. The pinched cone conformation of syn-2(2),4(2)-dihydroxy-1(2),3(2)-bis(prop-2-enyloxy)thiacalix[4]arene, C30H24O4S4, (3a), is stabilized by two intramolecular hydrogen bonds, remarkably formed from both OH groups to the same ether O atom. In syn-2(2),4(2)-dihydroxy-1(5),2(5),3(5),4(5)-tetranitro-1(2),3(2)-bis(prop-2-enyloxy)thiacalix[4]arene acetone disolvate, C30H20N4O12S4.2C3H6O, (3b1), the molecule is found in the 1,3-alternate conformation. The crystallographic C2 symmetry is due to a twofold rotation axis running through the centre of the calixarene ring. The hydroxy groups cannot form intramolecular hydrogen bonds as in (3a) and both are bonded to an acetone solvent molecule. The molecule of the pseudo-polymorph of (3b1) in which the same compound crystallized without any solvent, viz. (3b2), is located on a crystallographic mirror plane. Only one of the two hydroxy groups forms a hydrogen bond, and this is with a nitro group of a neighbouring molecule as acceptor. Molecular mechanics calculations for syn-1,3-diethers suggest a preference of the 1,3-alternate over the usual cone conformation for thiacalix[4]arene versus calix[4]arene and for para-nitro versus para-H derivatives.