Abstract
<jats:p>Perfluorophenazine (PFP), a bis-aza perfluoroarene, was co-crystallized with a series of polynuclear aromatic hydrocarbons; naphthalene, anthracene, phenanthrene, and tetracene, by slow evaporation from dichloromethane or 1-octanol. Single-crystal X-ray diffraction shows that, with the exception of the naphthalene adduct, each co-crystal adopts the cofacial, alternating-stack packing characteristic of arene–perfluoroarene systems, in contrast to the herringbone packing of PFP and each hydrocarbon component in their pure crystalline states. Inter-component inter-planar angles (0.85–4.92°), inter-centroid distances (3.34–3.79 Å), inter-planar distances (3.34–3.38 Å), slip angles (12.8–27.4°), slip distances, and C–H···F–C contact geometries (2.48–2.65 Å) were determined for each complex and compared across the series. These results extend the established structural systematics of arene–perfluoroarene co-crystallization, previously documented almost exclusively for all-carbon perfluoroarenes, to an aza-substituted perfluoroarene, and indicate that ring nitrogen substitution does not disrupt the cofacial packing preference.</jats:p>