X-ray diffraction study of the disorder-to-order transition at ~160 K in the π-molecular compound pyrene···pyromellitic dianhydride

Abstract

The crystal structure of pyrene...pyromellitic dianhydride [(C_(16)H_(10):C_(10)H_2O_6); PYRPMA] has been studied over the range 300-19K, using the low-temperature accessory designed by Samson, Goldish & Dick [J. Appl. Cryst. (1980), 13, 425-432] for a four-circle diffractometer. Earlier results for the disordered and ordered structures [Herbstein & Snyman (1969). Philos. Trans. R. Soc. London Ser. A, 264, 635-666] are confirmed and extended. At 295 K, a = 13.94 (1), b = 9.34 (1), c = 7.31 (1) Å, β = 93.65 (9)°, space group P2_l/a, Z = 2, with pyrenes and pyromellitic dianhydrides (PMDAs) at crystallographic centres of symmetry. At 19 K, a = 13.664 (3), b = 9.281 (2), c = 14.420 (3)Å, β = 91.80 (2)°, space group P2_l/n, Z = 4, with two sets of pyrenes at independent centres of symmetry and the four PMDAs at general positions. There are no discontinuities in cell dimensions with temperature (measurements at ~10K intervals, down to 19 K) but db/dT and dβ /dT show discontinuities at ~167 K. Superlattice reflections appear below ~164K (= T_c by X-ray diffraction), corresponding to the doubling of c and change of space group; the specific heat shows an anomalous increase over the range 120-155K, giving a λ-type peak. These results show that the transition is second order with regard to Ehrenfest's criteria. PYRPMA is a co-elastic crystal and quantitative analysis shows a linear dependence of the squares of spontaneous strain and of normalized superlattice intensity on temperature; hence, in terms of Landau theory, the transition is tricritical. However, the excess specific heat cannot be explained entirely on this basis. The physical nature of the transition is discussed. PYRPMA is so far unique among the π-molecular compounds showing disorder-to-order transitions in the solid state in that there is a doubling of one of the axes; all indications are, however, that it resembles the other examples in the sense that subtle intermolecular packing interactions (here between pyrenes and PMDAs) are the driving force for the transition rather than electronic or charge-transfer interactions.

Additional Information

© 1994 International Union of Crystallography. (Received 2 August 1993; accepted 21 October 1993) This work has been supported by the Fund of the Vice President for Research and the Fund for Promotion of Research at Technion, by the CSIR (Pretoria) and by a number of NIH grants. We are grateful to Drs Jessen & Küppers (Kiel) for a copy of their thermal expansion program, Dr Abraham Banai (Mathematics, Technion) for writing the BASIC program used for obtaining Fig. 4 and Dr L. A. K. Staveley (Oxford) and Professor E. F. Westrum Jr (Ann Abor) for useful comments on the thermodynamics. The referees have also been very helpful.

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