Cation-Cation Pairing by N-C-H•••O Hydrogen Bonds

The pairing of ions of opposite charge is a fundamental principle in chemistry, and is widely applied in synthesis and catalysis. In contrast, cation-cation association remains an elusive concept, lacking in supporting experimental evidence. While studying the structure and properties of 4-oxopiperidinium salts [OC5H8NH2]X for a series of anions X- of decreasing basicity, we observed a gradual self-association of the cations, concluding in the formation of an isolated dicationic pair. In 4-oxopiperidinium bis(trifluoromethylsulfonyl)amide, the cations are linked by NHOC hydrogen bonds to form chains, flanked by hydrogen bonds to the anions. In the tetra(perfluoro-tert-butoxy)aluminate salt, the anions are fully separated from the cations, and the cations associate pairwise by NCHOC hydrogen bonds. The compounds represent the first genuine examples of self-association of simple organic cations based merely on hydrogen bonding as evidenced by X-ray structure analysis, and provide a paradigm for an extension of this class of compounds.