Synergistic effects of hydrogen and halogen bonding in co-crystals of dipyridylureas and diiodotetrafluorobenzenes

Abstract

Herein, we investigate co-crystallization of three linear co-formers that contain urea and pyridyl groups with three regioisomers of diiodotetrafluorobenzene (DITFB) to afford eleven co-crystals. The linear o-, m-, and p- dipyridylureas vary distance and geometry between the urea carbonyl oxygen and two pyridyl nitrogen acceptors, while the donors consist of urea NH groups and the activated halides in DITFB. Electrostatic potential calculations suggest that the o-dipyridylurea co-former presents two significantly different acceptors. In comparison, the acceptors in the m- and p-dipyridylurea co-formers display electrostatic potentials within 5–6 kJ/mol and should be competitive, potentially leading to altered assembly motifs. Overall, ten of the co-crystals consistently display the urea assembly motif as the best acceptor/donor pair. Seven structures were obtained as the predicted 1:1 ratio with halogen bonding interactions linking ditopic halogen bond donors and the pyridyl units through N···I interactions ranging from 78.4 to 83.1% of the van der Waals radii. Modified structures were more likely when there was a structural mismatch with the geometrically challenging o-DITFB donor and m- or p-dipyridylurea co-former. The majority of the co-crystal structures (10/11) demonstrated fully satisfied hydrogen and halogen bonding interactions suggesting that these synthons can be used synergistically to generate complex solid-state structures.