Eccles, KS;Morrison, RE;Stokes, SP;O'Mahony, GE;Hayes, JA;Kelly, DM;O'Boyle, NM;Fabian, L;Moynihan, HA;Maguire, AR;Lawrence, SE

2012

June

Crystal Growth & Design

Utilizing Sulfoxide center dot center dot center dot lodine Halogen Bonding for Cocrystallization

Validated

WOS: 24 ()

CAMBRIDGE STRUCTURAL DATABASE CRYSTAL-STRUCTURES PHARMACEUTICAL COCRYSTALS ORGANIC FLUORINE BASIS-SET THIANTHRENE CONVENIENT THIOETHERS COMPLEXES OXIDATION

12

2969

2977

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

WASHINGTON

1528-7483

10.1021/cg300189v