In-situ high-pressure study of the ordered phase of ethyl propionate

Ethyl propionate, C5H10O2 (m.p. 199 K), has been in-situ pressure-frozen and its structure determined at 1.34, 1.98 and 2.45 GPa. The crystal structure of the new high-pressure phase (denoted beta) is different from phase alpha obtained by lowering the temperature. The freezing pressure of ethyl propionate at 296 K is 1.03 GPa. The molecule assumes an extended chain s-trans-trans-trans conformation, only slightly distorted from planarity. The closest intermolecular contacts in both phases are formed between carbonyl O and methyl H atoms; however, the ethyl-group H atoms in phase beta form no contacts shorter than 2.58 angstrom. A considerable molecular volume difference of 24.2 angstrom(3) between phases alpha and beta can be rationalized in terms of degrees of freedom of molecules arranged into closely packed structures: the three degrees of freedom allowed for rearrangements of molecules confined to planar sheets in phase et, but are not sufficient for obtaining a densely packed pattern.