cg501210t_si_004.cif (852.6 kB)

Isostructural Co-crystals Derived from Molecules with Different Supramolecular Topologies

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posted on 05.11.2014, 00:00 by Michael C. Pfrunder, Aaron S. Micallef, Llewellyn Rintoul, Dennis P. Arnold, Karl J. P. Davy, John McMurtrie
In this article, we report the crystal structures of five halogen bonded co-crystals comprising quaternary ammonium cations, halide anions (Cl and Br), and one of either 1,2-, 1,3-, or 1,4-diiodotetrafluorobenzene (DITFB). Three of the co-crystals are chemical isomers: 1,4-DITFB­[TEA-CH2Cl]­Cl, 1,2-DITFB­[TEA-CH2Cl]­Cl, and 1,3-DITFB­[TEA-CH2Cl]Cl (where TEA-CH2Cl is chloromethyltriethylammonium ion). In each structure, the chloride anions link DITFB molecules through halogen bonds to produce 1D chains propagating with (a) linear topology in the structure containing 1,4-DITFB, (b) zigzag topology with 60° angle of propagation in that containing 1,2-DITFB, and (c) 120° angle of propagation with 1,3-DITFB. While the individual chains have highly distinctive and different topologies, they combine through π-stacking of the DITFB molecules to produce remarkably similar overall arrangements of molecules. Structures of 1,4-DITFB­[TEA-CH2Br]Br and 1,3-DITFB­[TEA-CH2Br]Br are also reported and are isomorphous with their chloro/chloride analogues, further illustrating the robustness of the overall supramolecular architecture. The usual approach to crystal engineering is to make structural changes to molecular components to effect specific changes to the resulting crystal structure. The results reported herein encourage pursuit of a somewhat different approach to crystal engineering. That is, to investigate the possibilities for engineering the same overall arrangement of molecules in crystals while employing molecular components that aggregate with entirely different supramolecular connectivity.