Ortho‐Substituent Effects on Halogen Bond Geometry for N‐Haloimide⋯2‐Substituted Pyridine Complexes

The nature of (imide)N–X⋯N(pyridine) halogen‐bonded complexes formed by six N‐haloimides and sixteen 2‐substituted pyridines are studied using X‐ray crystallography (68 crystal structures), Density Functional Theory (DFT) (86 complexation energies), and NMR spectroscopy (90 association constants). Strong halogen bond (XB) donors such as N‐iodosuccinimide form only 1:1 haloimide:pyridine crystalline complexes, but even stronger N‐iodosaccharin forms 1:1 haloimide:pyridine and three other distinct complexes. In 1:1 haloimide:pyridine crystalline complexes, the haloimide's N─X bond exhibits an unusual bond bending feature that is larger for stronger N‐haloimides. DFT complexation energies (ΔEXB) for iodoimide–pyridine complexes range from −44 to −99 kJ mol−1, while for N‐bromoimide–pyridine, they are between −31 and −77 kJ mol−1. The ΔEXB of I⋯N XBs in 1:1 iodosaccharin:pyridine complexes are the largest of their kind, but they are substantially smaller than those in [bis(saccharinato)iodine(I)]pyridinium salts (−576 kJ mol−1), formed by N‐iodosaccharin and pyridines. The NMR association constants and ΔEXB energies of 1:1 haloimide:pyridine complexes do not correlate as these complexes in solution are heavily influenced by secondary interactions, which DFT studies do not account for. Association constants follow the σ‐hole strengths of N‐haloimides, which agree with DFT and crystallography data. The haloimide:2‐(N,N‐dimethylamino)pyridine complex undergoes a halogenation reaction resulting in 5‐iodo‐2‐dimethylaminopyridine. Comprehensive analysis of N‐haloimides and 2‐substituted pyridine N−X···N halogen‐bonded complexes (68 crystal structures, 102 Density Functional Theory (DFT) optimized structures, and 90 1H NMR association constants) reveals unusual packing forces induced N−X bond bendings and N···X···N motifs symmetrization in crystals, and DFT bond energies tunability on sigma‐hole strengths.