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Do halogen bonds dictate the packing preferences in solid solutions?

Pramanik, Titas and Pavan, Mysore S and Row, Tayur N Guru (2017) Do halogen bonds dictate the packing preferences in solid solutions? In: FARADAY DISCUSSIONS, 203 . pp. 201-212.

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Official URL: http://doi/10.1039/c7fd00084g

Abstract

The isomeric compounds, 4-bromo-2-chloro benzoic acid (4Br) and 2-bromo-4-chlorobenzoic acid (2Br), crystallize in entirely different space groups, P2(1)/n and P (1) over bar respectively. Both structures are stabilized by a strong O-H center dot center dot center dot O hydrogen bonds generating a carboxylic acid dimer along with an unusual triangular halogen bonded motif in the former and a well-defined halogen bond in the latter. Charge density analysis establishes the nature of halogen bonds by bringing out significant changes in the packing features of the two structures as well as the quantification of the interaction energies involved in the formation of the motifs. Cocrystallization efforts lead to the formation of solid solutions of varied stoichiometric ratios among the two entirely different crystalline forms, a feature which is observed for the first time, and depends on the nature of the halogen bonds. Despite the significant variations in the charge density distribution in intermolecular space, the triangular motif, with two type II Br center dot center dot center dot Cl and Cl center dot center dot center dot Br and one type I Br center dot center dot center dot Br contact in the structure of 4Br dictates the packing preferences in the solid solution as established by accurate single crystal diffraction studies supported by cognate powder diffraction analysis (PXRD) and differential scanning calorimetric (DSC) studies. A systematic study of the solid solution by varying the stoichiometric ratios establishes the hierarchy in halogen bonded motifs and consequently its directional influence to form the resultant supramolecular assembly.

Item Type: Journal Article
Additional Information: Copy right for this article belongs to theROYAL SOC CHEMISTRY, THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLAND
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Depositing User: Id for Latest eprints
Date Deposited: 03 Nov 2017 10:42
Last Modified: 03 Nov 2017 10:42
URI: http://eprints.iisc.ac.in/id/eprint/58164

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