This quadrupolar electrostatics viewpoint on π-stacking exemplifies how electrostatic considerations dominate the thinking in organic chemistry, and how leading-order multipolar interactions are often used as surrogates for electrostatics. Not only does the multipolar picture disagrees with exact electrostatics at π-stacking distances (predicting even the wrong sign for E elst at R = 3.4 Å separation), it also cannot explain the origin of parallel-displaced π-stacking in the (C 6 H 6 )• • • (C 6 F 6 ) heteromolecular dimer. This phenomenon emerges from calculations, 235 as illustrated in Fig. . For a symmetric top molecule, the quadrupole moment tensor has only one independent component (call it Θ zz ), Edge-to-Face Face-to-Face