Treatment of (C 6 F 5 ) 2 Zn(toluene) with 2 equiv of a series of benzonitrile or pyridine derivatives yielded the complexes (C 6 F 5 ) 2 Zn(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 19 F NMR experiments and comparison to (C 6 F 5 ) 2 Zn(2,2′-bipy). The solvent-free solid-state structures of each of the four-coordinate adducts and the toluene solvate of (C 6 F 5 ) 2 Zn(NCC 6 H 4 C 6 H 5 ) 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.