Abstract
The propensity of C—F groups to form \( \mathrm{C}\mathrm{F}\cdots \mathrm{H}\mathrm{C} \) interactions with C—H groups on other molecules has been analyzed. Crystal structures of molecules containing only carbon, hydrogen, and fluorine, but no oxygen, nitrogen, or other hydrogen-bond-forming elements, were chosen for an initial study in which the intermolecular interactions in crystal-structure determinations of polycyclic aromatic hydrocarbons and their analogous fluoro derivatives were analyzed. It is found that \( \mathrm{C}\mathrm{F}\cdots \mathrm{H}\mathrm{C} \) interactions occur, but they are weak, as judged by the intermolecular distances and the angles involved. In a study of crystal structures of molecules containing other elements in addition to carbon, hydrogen, and fluorine, it was found that when an oxygen atom is in a neighboring position on an interacting molecule, a C—O group is more likely than a C—F group to form a linear interaction to the hydrogen atom of a C—H group. Thus, in spite of the high electronegativity of the fluorine atom, a C—F group competes unfavorably with a C—O−, C—OH or C═O group to form a hydrogen bond to an O—H, N—H, or C—H group. It is found, however, particularly for polycyclic aromatic hydrocarbons with substituted CF3 groups that, in the absence of other functional groups that can form stronger interactions, \( \mathrm{C}\mathrm{F}\cdots \mathrm{H}\mathrm{C} \) interactions may serve to align molecules and give a different crystal packing from that in the pure hydrocarbon (where fluorine is replaced by hydrogen). Thus, \( \mathrm{C}\mathrm{F}\cdots \mathrm{H}\mathrm{X}\left(\mathrm{X}=\mathrm{C},\mathrm{N},\mathrm{O}\right) \) interactions are very weak, much weaker than C═O\( \cdots \mathrm{H}\mathrm{X} \) interactions, but they cannot be ignored in predictions of modes of molecular packing in complexes and in crystals.
Keywords
Structural Chemistry 1994, 5(6):383–397.
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Acknowledgments
We want to thank Ms. Doree Sitkoff (from the Department of Biochemistry and Molecular Biophysics at Columbia University Health Sciences) for calculating the electron charge distribution and for fruitful discussions concerning this paper. This work was supported by NIH grants GM-44360 and CA-06927 and by an appropriation from the Commonwealth of Pennsylvania.
Supplementary Material Available
Tables 1, 2, 3, 4, and 5 and the list of CSD reference codes and bibliographical information on crystal structures in this study are available from National Auxiliary Publications Service, c/o Microfische Publications. P.O. Box 3513, Grand Central Station, New York, NY 10163-3513. (NAPS Document No. 05160, consisting of 39 pages.)
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Shimoni, L., Glusker, J.P. (2015). The Geometry of Intermolecular Interactions in Some Crystalline Fluorine-Containing Organic Compounds. In: Hargittai, I., Hargittai, B. (eds) Science of Crystal Structures. Springer, Cham. https://doi.org/10.1007/978-3-319-19827-9_21
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DOI: https://doi.org/10.1007/978-3-319-19827-9_21
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