Stereoelectronic effects of substituent groups in the solid state. Crystal chemistry of some cubanecarboxylic and phenylpropiolic acids

Das, Dinabandhu ; Jetti, Ram K. R. ; Boese, Roland ; Desiraju, Gautam R. (2003) Stereoelectronic effects of substituent groups in the solid state. Crystal chemistry of some cubanecarboxylic and phenylpropiolic acids Crystal Growth & Design, 3 (5). pp. 675-681. ISSN 1528-7483

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Official URL: http://pubs.acs.org/doi/abs/10.1021/cg0341252

Related URL: http://dx.doi.org/10.1021/cg0341252

Abstract

A series of 4-substituted cubanecarboxylic acids and phenylpropiolic acids have been studied with the aim of elucidating steric and electronic factors exerted by the 4-substituent in the formation of the dimer, or alternatively, the rare syn-anti catemer patterns in their respective crystal structures. It is shown that catemer formation depends critically on the ability of a proximal C-H group to form a supportive C-H···O bond. In turn, this means that the C-H group must be sufficiently activated toward hydrogen bond formation. Such activation is inherent to the cubyl group but must be present additionally from a suitable electron withdrawing group in the phenylpropiolic acids. In any event, while C-H activation is necessary for catemer formation it is not sufficient. The substituent group that is present in the 4-position must also be sufficiently bulky so as to form a close packed array that is compatible with the catemer geometry. These trends are justified by the crystal structures of the 12 acids in the two families wherein the 4-substituent group is H, F, Cl, Br, I, and CH3. Our results indicate that electronic and steric effects of functional groups may be distinguished in the solid state, in that the formation of either a dimer or catemer may be rationalized on the basis of these effects.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:11572
Deposited On:13 Nov 2010 17:01
Last Modified:30 May 2011 09:52

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