By Eccles, Kevin S.; Morrison, Robin E.; Stokes, Stephen P.; O'Mahony, Graham E.; Hayes, John A.; Kelly, Dawn M.; O'Boyle, Noel M.; Fabian, Laszlo; Moynihan, Humphrey A.; Maguire, Anita R, Lawrence, Simon E.

2012

Crystal Growth & Design

Utilizing Sulfoxide•••Iodine Halogen Bonding for Cocrystallization

Published

()

12

6

2969

2977

The propensity of a range of different sulfoxides and sulfones to cocrystallize with either 1,2- or 1,4-diiodotetrafluorobenzene, via I···O=S halogen bonding, was investigated.  Cocrystn. occurred exclusively with 1,4-diiodotetrafluorobenzene in either a 1:1 or 1:2 stoichiometry of the organohalide and the sulfoxide, resp., depending on the sulfoxide used.  It was found that the stoichiometry obsd. was not necessarily related to whether the oxygen acts as a single halogen bond acceptor or if it is bifurcated; with I···π interactions obsd. in two of the cocrystals synthesized.  Only those cocrystals with a 1:2 stoichiometry exhibit C-H···O hydrogen bonding in addn. to I···O=S halogen bonding.  Examn. of the Cambridge Structural Database shows that (i) the I···O=S interaction is similar to other I···O interactions, and (ii) the I···π interaction is significant, with the distances in the two cocrystals among the shortest known.

DOI:10.1021/cg300189v