Evolution of Cocrystals from Solid Solutions in Benzoic Acid-Mono/poly-fluorobenzoic Acid Combinations

Seera, R and Cherukuvada, S and Guru Row, TN (2021) Evolution of Cocrystals from Solid Solutions in Benzoic Acid-Mono/poly-fluorobenzoic Acid Combinations. In: Crystal Growth and Design .

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Abstract

Benzoic acid-monofluorobenzoic acid combinations are known to form solid solutions, whereas benzoic acid-pentafluorobenzoic acid system forms a cocrystal. To decipher the gradation from solid solution to cocrystal between these extremes, we executed the cocrystallization of benzoic acid with several of its poly-fluoro (di-, tri-, and tetra-) substituents. The fluorine atom, with its sheer geometric position and intermolecular (hydrogen and halogen) bonding ability, is found to steer the transformation from a solid solution to a cocrystal in this family of compounds. We found, among others, a novel crystal entity in the benzoic acid-3,4,5-trifluorobenzoic acid combination that shows characteristics of both a solid solution (a single disordered molecule in the crystallographic asymmetric unit) and a cocrystal (a distinct crystal structure as compared with the parent compounds). This solid solution-cum-cocrystal therefore acts a connecting link in the evolution of cocrystals from solid solutions in benzoic acid-fluorobenzoic acid systems. In addition, the cocrystallization of benzoic acid with 2,6-difluorobenzoic acid and 2,4,6-trifluorobenzoic acid resulted in eutectics, which appears to be due to the supramolecular incompatibility invoked by out-of-plane carboxylic acid in the latter compounds. © 2021 American Chemical Society.

Item Type:	Journal Article
Publication:	Crystal Growth and Design
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society
Keywords:	Crystal structure; Halogen compounds; Mathematical transformations; Solid solutions, Asymmetric unit; Bonding ability; Cocrystallization; Disordered molecules; Fluorine atoms; Fluorobenzoic acids; Geometric position; Parent compounds, Benzoic acid
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	29 Nov 2021 11:17
Last Modified:	29 Nov 2021 11:17
URI:	http://eprints.iisc.ac.in/id/eprint/70002

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