Halides with Fifteen Aliphatic C–H···Anion Interaction Sites

Since the aliphatic C–H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C–H (C(ali)–H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic C(ali)–H groups. An X-ray structure of imidazolium-based scaffolds using C(ali)–H···A(−) interactions (A(−) = anion) shows that a halide anion is directly interacting with fifteen C(ali)–H groups (involving eleven hydrogen bonds, two bidentate hydrogen-bond-type binding interactions and two weakly hydrogen-bonding-like binding interactions). Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The C(ali)–H···A(−) interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms.