C-H···O interactions and the adoption of 4 Å short-axis crystal structures by oxygenated aromatic compounds

Sarma, Jagarlapudi A. R. P. ; Desiraju, Gautam R. (1987) C-H···O interactions and the adoption of 4 Å short-axis crystal structures by oxygenated aromatic compounds Journal of the Chemical Society, Perkin Transactions 2 (9). pp. 1195-1202. ISSN 0300-9580

Full text not available from this repository.

Official URL: http://www.rsc.org/publishing/journals/P2/article....

Related URL: http://dx.doi.org/10.1039/P29870001195


Oxygen atoms, pendant as substituents or occurring within the ring systems of planar aromatic molecules, have a pronounced tendency to direct crystallisation patterns of such compounds to the β -structure, characterised by a 4 Åshort axis. They seem to perform this function by stabilising a critical number of hydrogen atoms, covalently bonded to carbon, through short and directionally specific intermolecular C-H···O hydrogen bonds. Consequently, the number of free hydrogen atoms which contribute to crystal stabilisation through non-β steering C H interactions is reduced. Both these factors result in the formation of C-H…O stabilised two-dimensional entities such as sheets and ribbons. Such entities may be stacked at 4 Å translational separation to generate the entire structure. These concepts are illustrated for some methylenedioxy and alkoxy aromatic systems, quinones, and heterocycles. However, both intra- and inter-sheet C-H…O interactions may sometimes be present and the unusual crystal structure of 7-acetoxycoumarin (5) shows how a significantly non-planar molecule may still adopt the β-structure if it is particularly well suited for the formation of C-H···O bonds. Yet 4-acetoxycinnamic acid (6), the crystal structure of which was determined in this work and which has almost the same C:H:O ratio as (5), adopts a non-β structure because the number of oxygen atoms available for C-H···O bond formation is greatly reduced. The crucial role of the number of such available oxygen atoms and H-bonded and free(C-)H atoms vis-à-vis the carbon content is exemplified by the β-steering behaviour of oxygen in some large fused-ring quinones and heterocycles. These trends may also be extended to nitrogen and sulphur heterocycles.

Item Type:Article
Source:Copyright of this article belongs to Royal Society of Chemistry.
ID Code:11003
Deposited On:09 Nov 2010 04:18
Last Modified:28 May 2011 11:27

Repository Staff Only: item control page