Supramolecular Synthesis Based on a Combination of Hydrogen and Halogen Bonds

A family of supramolecular reagents containing two different binding sites, pyridine and amino-pyrimidine, were allowed to react with iodo- or bromo-substituted benzoic acids in order to assemble individual molecules into larger architectures with precise intermolecular interactions, using a combination of hydrogen- and halogen-bonds. The hydrogen-bond based amino-pyrimidine/carboxylic acid or amino-pyrimidinium/carboxylate synthons are responsible for the assembly of the primary structural motif in every case (7/7 times, 100% supramolecular yield), while I center dot center dot center dot N, Br center dot center dot center dot N, and I center dot center dot center dot O, halogen bonds play a structural supporting role by organizing these supermolecules into extended 1D and 2D architectures (5/7 times, 71% supramolecular yield). These results illustrate how two different noncovalent interactions can be employed side-by-side in the reliable construction of extended molecular solid-state networks with predictable connectivity and dimensionality.