Crystal structure of piperazinium oleate at -150 degrees C.

Abstract

The crystal structure of piperazinium oleate ([C4H12N2]2+.2[C18H34O2]-) has been determined from X-ray diffraction data at -150 degrees C in order to study the oleate chain conformation and molecular packing. Differential scanning calorimetry shows three reversible crystalline state phase transitions (54.5, -34.8, and -54.8 degrees C) in the range from the melting point (84.8 degrees C) to -160 degrees C. The cell constants for a flash-frozen crystal at -150 degrees C are a = 5.630(2), b = 14.900(2), c = 24.825(4) A, alpha = 88.77(2), beta = 88.12(2), gamma = 80.38(2) degrees; Z = 2, space group P1; Dc = 1.05 g cm-3, m.p. = 84.8 degrees C. The cell constants are similar at room temperature except for a doubling of b at -150 degrees C. The crystal structure at -150 degrees C has been refined to R(F2) = 0.116 for 8410 independent reflections. There are two independent oleate anions (A and B), both having an overall extended conformation except for kinks that are different at the cis olefin group. The oleate A chain is ordered while the oleate B chain is disordered in two regions. Because of different torsion angles at bonds adjacent to the double bond, the B-chain olefin group adopts two configurations, one of which is predominant. From the olefin group to the terminal methyl group, the B-chain adopts one of two all-trans configurations with equal probability. It cannot be determined whether the two kinds of disorder are correlated. Taking into account the centrosymmetrically related oleate chains, the crystal structure contains at least six and possibly eight extended chain conformers with different kinks at the olefin group. Third and fourth order displacement parameters have been determined for the partially resolved atomic sites in the oleate B chain and these have been used to map probability density functions for the disordered atoms. The piperazinium cations are in a chair conformation. Each is hydrogen bonded to four oleate anions, forming an infinite ribbon parallel to (025). These ribbons are stacked upon each other to form a monolayer 24.8 A thick parallel to (001).