Triple Activation Facilitates Modular and Stoichiometric Control over Cocrystals of Phenazine

Robust and reliable synthons can facilitate the synthesis of predictable and complex supramolecular assemblies. In this study, we employ triply activated halogen-bond donors as a driver for cocrystal formation and examine the influence of the sigma-hole potential for controlling the stoichiometry of binary cocrystals of phenazine. Six new crystal structures are presented for ketone:phenazine binary cocrystals as well as six crystal structures for ester:phenazine cocrystals. The combination of structural chemistry and theory provides an increased understanding of how controlled variation of the molecular electrostatic potential on the halogen-bond atom can control the stoichiometry in the resulting binary cocrystals.