Electron conjugation versus π-π repulsion in substituted benzenes: why the carbon-nitrogen bond in nitrobenzene is longer than in aniline.

Gas-phase electron diffraction experiments show that the C-N bond in aniline (1.407 Å) is significantly shorter than in nitrobenzene (1.486 Å). It is known that the amino group is electron-donating and the nitro group is electron-withdrawing, and both substitution groups can effectively conjugate with benzene. Thus, it is puzzling why the C-N bond in nitrobenzene is even longer than the single C-N bond in methylamine (1.472 Å). In this work, we performed computations by strictly localizing the π electrons with the block-localized wavefunction (BLW) method, which is a variant of ab initio valence bond theory. Geometry optimizations of electron-localized states, where the conjugation over the C-N bond is quenched, show that the conjugation in nitrobenzene is only half of the conjugation in aniline. But even in optimal electron-localized states, the C-N bond in nitrobenzene is still 0.074 Å longer than in aniline. As a consequence, it is indeed not the π conjugation which is responsible for the disparity of the C-N bond distances in these systems. Instead, we demonstrated that the π-π repulsion, which is contributed by both Pauli exchange and electrostatic interaction, plays the key role in this "abnormal" behavior. Notably, the π resonance within the nitro group generates a considerable dipole, which repels the π electrons in the benzene ring. The deactivation of the resonance within the nitro group significantly shortens the C-N bond by 0.06 Å. The unfavorable π-π electrostatic repulsion is further exemplified by N2O4. In fact, the destabilizing π-π repulsion is ubiquitous but largely neglected in conjugated systems where only the stabilizing conjugation is the focus. Experimental phenomena such as the C-N bond distances in aniline and nitrobenzene result from the balance of both stabilizing and destabilizing forces.