Arylethynyl Helices Supported by π-Stacking and Halogen Bonding

Co-crystallization of a pyridyl-containing arylethynyl (AE) moiety with 1,4-diiodotetrafluorobenzene leads to unique, figure-eight shaped helical motifs within the crystal lattice. A slight twist in the AE backbone allows each AE unit to simultaneously interact with haloarene units that are stacked on top of one another. Left-handed (M) and right-handed (P) helices are interspersed in a regular pattern throughout the crystal. The major driving forces for assembly are 1) halogen bonding between the pyridyl nitrogen atoms and the iodine substituents of the haloarene, with N⋅⋅⋅I distances between 2.81 and 2.84 Å, and 2) π-π stacking of the haloarenes, with distances of approximately 3.57 Å between centroids. Halogen bonding and π-π stacking not only work in concert, but also seem to mutually enhance one another. Calculations suggest that the presence of π-π stacking modestly intensifies the halogen bonding interaction by <0.2 kcal/mol; likewise, halogen bonding to the haloarene enhances the π-π stacking interaction by 0.59 kcal/mol.