Azulene revisited: solid‐state structure, invariom modeling and lattice‐energy minimization of a classical example of disorder

• Published in: Acta crystallographica Section B, Structural science, crystal engineering and materials Structural science, crystal engineering and materials, 2018-10, Vol.74 (5), p.416-426
• Main Authors: Dittrich, B., Fabbiani, F. P. A., Henn, J., Schmidt, M. U., Macchi, P., Meindl, K., Spackman, M. A.
• Format: Article
• Language: English
• Subjects: Azulene; Crystal structure; DFT calculations; Dipole moments; disorder; Electron density; Electron diffraction; Energy conservation; invariom modeling; Lattice energy; lattice‐energy minimization; Mathematical models; Molecular structure; Parameters; Superposition (mathematics); Symmetry; X-ray diffraction
• ISSN: 2052-5206; 2052-5192; 2052-5206
• DOI: 10.1107/S2052520618010120

The molecular and solid‐state structure of azulene both raise fundamental questions. Therefore, the disordered crystal structure of azulene was re‐refined with invariom non‐spherical atomic scattering factors from new single‐crystal X‐ray diffraction data with a resolution of d = 0.45 Å. An unconstrained refinement results in a molecular geometry with Cs symmetry. Refinements constrained to fulfill C2v symmetry, as observed in the gas phase and in high‐level ab initio calculations, lead to similar figures of merit and residual densities as unconstrained ones. Such models are consistent with the structures from microwave spectroscopy and electron diffraction, albeit they are not the same. It is shown that for the disorder present in azulene, the invariom model describes valence electron density as successfully as it does for non‐disordered structures, although the disorder still leads to high correlations mainly between positional parameters. Lattice‐energy minimizations on a variety of ordered model structures using dispersion‐corrected DFT calculations reveal that the local deviations from the average structure are small. Despite the molecular dipole moment there is no significant molecular ordering in any spatial direction. A superposition of all ordered model structures leads to a calculated average structure, which explains not only the experimental determined atomic coordinates, but also the apparently unusual experimental anisotropic displacement parameters. Azulene, the classical example of a disordered structure, is revisited. Aspherical‐atom least‐squares refinement of high‐resolution diffraction data is complemented with lattice‐energy computations of model structures.