Synthesis, Structure, and Supramolecular Architecture of Benzonitrile and Pyridine Adducts of Bis(pentafluorophenyl)zinc: Pentafluorophenyl–Aryl Interactions versus Homoaromatic Pairing

Treatment of (C6F5)2Zn(toluene) with 2 equiv of a series of benzonitrile or pyridine derivatives yielded the complexes (C6F5)2Zn(L)2 (where L = benzonitrile, 4-(phenyl)benzonitrile, 4-(N-pyrrolyl)benzonitrile, pyridine, 4-(phenyl)pyridine, and 4-(N-pyrrolyl)pyridine). The four-coordinate solution-phase nature of these complexes was confirmed by a series of variable-temperature 19F NMR experiments and comparison to (C6F5)2Zn(2,2′-bipy). The solvent-free solid-state structures of each of the four-coordinate adducts and the toluene solvate of (C6F5)2Zn(NCC6H4C6H5)2 were determined by single-crystal X-ray diffraction and have distorted tetrahedral geometries. Analysis of the crystal packing revealed a preponderance of offset face-to-face homo−aryl and embrace-like interactions over the hetero−aryl, pentafluorophenyl−phenyl, interaction. These aryl−aryl synthons serve to assemble paired, one- and three-dimensional supramolecular architectures.