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Shimoni L , Glusker JP
The Geometry of Intermolecular Interactions in Some Crystalline Fluorine-Containing Organic-Compounds
Structural Chemistry. 1994 Dec;5(6) :383-397
PMID: ISI:A1994PT75700006   
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The propensity of C-F groups to form C-F...H-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 C-F...H-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, C-F...H-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, C-F...H-X (X=C, N, O) interactions are very weak, much weaker than C=O...H-X interactions, but they cannot be ignored in predictions of modes of molecular packing in complexes and in crystals.
English Article PT757 STRUCT CHEM