Abstract
PREVIOUS work on the crystal structure of azulene1 has shown that the apparent space group is P21/a (C 5 2h) with two molecules in the unit cell. This implies a centrosymmetric molecule, which is in conflict with the chemical evidence. The two most likely explanations of this discrepancy are: (a) that the implied centre of symmetry is only statistically true, and is due to rotating molecules or a disordered structure; or (b) that the absent spectra leading to the deduction of the space group P21/a are accidental, and that the true space group is really of lower symmetry. Günthard2 has discussed these possibilities, and in recent work3 has shown that a comparison of the entropies of azulene and naphthalene (which has similar lattice dimensions) appears to confirm the presence of some disorder in the azulene crystal.
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References
Günthard, H. H., Plattner, Pl. A., and Brandenberger, E., Experientia, 4, 425 (1948).
Günthard, H. H., Thèse Doc. Sci. tech. Zurich, Neographic, in 8° pp. 73 (1949).
Günthard, H. H., Helv. Chim. Acta, 38, 1918 (1955).
Wilson, A. J. C., Acta Cryst., 2, 318 (1949).
Howells, E. R., Phillip, D. C., and Rogers, D., Acta Cryst., 3, 210 (1950).
Robertson, J. M., Proc. Roy. Soc., A, 142, 674 (1933).
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ROBERTSON, J., SHEARER, H. Structure of Azulene. Nature 177, 885 (1956). https://doi.org/10.1038/177885a0
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DOI: https://doi.org/10.1038/177885a0
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