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A structural systematic study of four isomers of difluoro-N-(3-pyridyl)benzamide
McMahon, Joyce; Gallagher, John F.; Anderson, Frankie P.; Lough, Alan J.
The four isomers 2,4-, (I), 2,5-, (II), 3,4-, (III), and 3,5-difluoro-N-(3-pyridyl)benzamide, (IV), all with formula C12H8F2N2O, display molecular similarity, with interplanar angles between the C6/C5N rings ranging from 2.94 (11)° in (IV) to 4.48 (18)° in (I), although the amide group is twisted from either plane by 18.0 (2)-27.3 (3)°. Compounds (I) and (II) are isostructural but are not isomorphous. Intermolecular N-H...O=C interactions form one-dimensional C(4) chains along [010]. The only other significant interaction is C-H...F. The pyridyl (py) N atom does not participate in hydrogen bonding; the closest H...Npy contact is 2.71 Å in (I) and 2.69 Å in (II). Packing of pairs of one-dimensional chains in a herring-bone fashion occurs via [pi]-stacking interactions. Compounds (III) and (IV) are essentially isomorphous (their a and b unit-cell lengths differ by 9%, due mainly to 3,4-F2 and 3,5-F2 substitution patterns in the arene ring) and are quasi-isostructural. In (III), benzene rotational disorder is present, with the meta F atom occupying both 3- and 5-F positions with site occupancies of 0.809 (4) and 0.191 (4), respectively. The N-H...Npy intermolecular interactions dominate as C(5) chains in tandem with C-H...Npy interactions. C-H...O=C interactions form R22(8) rings about inversion centres, and there are [pi]-[pi] stacks about inversion centres, all combining to form a three-dimensional network. By contrast, (IV) has no strong hydrogen bonds; the N-H...Npy interaction is 0.3 Å longer than in (III). The carbonyl O atom participates only in weak interactions and is surrounded in a square-pyramidal contact geometry with two intramolecular and three intermolecular C-H...O=C interactions. Compounds (III) and (IV) are interesting examples of two isomers with similar unit-cell parameters and gross packing but which display quite different intermolecular interactions at the primary level due to subtle packing differences at the atom/group/ring level arising from differences in the peripheral ring-substitution patterns.
Keyword(s): Organic chemistry; Chemistry; Crystallography
Publication Date:
2009
Type: Other
Peer-Reviewed: Unknown
Language(s): English
Institution: Dublin City University
Citation(s): McMahon, Joyce, Gallagher, John F. ORCID: 0000-0003-4130-4556 <https://orcid.org/0000-0003-4130-4556>, Anderson, Frankie P. and Lough, Alan J. (2009) A structural systematic study of four isomers of difluoro-N-(3-pyridyl)benzamide. Acta Crystallographica Section C, 65 (7). pp. 345-351. ISSN 0108-2701
Publisher(s): International Union of Crystallography
File Format(s): application/pdf
Related Link(s): http://doras.dcu.ie/4635/1/acta_crys_c_65_7.pdf,
http://dx.doi.org/10.1107/S010827010902215X
First Indexed: 2009-11-05 02:01:33 Last Updated: 2019-02-09 06:58:52