C-H···F interactions in the crystal structures of some fluorobenzenes

Thalladi, Venkat R. ; Weiss, Hans-Christoph ; Blaser, Dieter ; Boese, Roland ; Nangia, Ashwini ; Desiraju, Gautam R. (1998) C-H···F interactions in the crystal structures of some fluorobenzenes Journal of the American Chemical Society, 120 (34). pp. 8702-8710. ISSN 0002-7863

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ja981198e

Related URL: http://dx.doi.org/10.1021/ja981198e


The existence and nature of C-H···F-C interactions in crystalline fluorobenzenes 1-3 and 7-10 are discussed. These compounds were chosen because they contain only C, H, and F atoms; this is necessary in the evaluation of the weak acceptor capabilities of the C-F group. All of these compounds are liquids at room temperature, and single crystals for X-ray diffraction were grown in situ. The analysis of the C-H···F interactions that are found in all of these crystal structures takes the form of comparisons with related C-H···O/C-H···N analogues. Fluorobenzene, 1, bears a close relationship to pyridinium fluoride, pyridine 1-oxide, and benzonitrile at the level of individual interactions, showing that the character of the structure-determining intermolecular interactions in these four crystal structures are the same. Similarly, 1,4-difluorobenzene, 3, and 1,4-benzoquinone are related, the C-H···F interactions in the former playing the same structural role as the C-H···O interactions in the latter. A comparison of 3 with the unsymmetrical 1,4-dihalogenated benzenes, 4-6 indicates the importance of C-H···F interactions in these structures. With an increase in the F content of the molecules, the C-H acidity also increases and the C-H···F interactions in 1,3,5-trifluorobenzene, 7, and 1,2,4,5-tetrafluorobenzene, 8, become stronger and more important. Compounds 7 and 8 are structurally very similar to 1,3,5-triazine and 1,2,4,5-tetrazine, and this similarity further strengthens the argument that C-H···F interactions resemble C-H···N interactions and provides evidence for their description as weak hydrogen bonds. 1,2,3,4-Tetrafluorobenzene, 9, is polymorphic but the role of the C-H···F interactions in the two forms is similar. A comparison of the C-H···F geometries in compounds 1-10 with other C-, H-, and F-containing compounds in the Cambridge Structural Database reveals that the hydrogen bond properties are more pronounced in 1-10. It is concluded that only when the carbon acidity is enhanced to the levels of the compounds in the present study, is the hydrogen-bond nature of the C-H···F interaction even revealed. This study also demonstrates that the C-F group prefers to form C-H···F interactions rather than F···F contacts. The behavior of organic fluorine in crystal packing is therefore quite different from the heavier halogens.

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