The good halogen bond donor N-bromosaccharin (NBrSac) has been cocrystallized with four para-substituted pyridines (PyX) as acceptors of different strengths (PyCN, PyCF3, PyCO2Me, and PyMe). Their crystal structures have determined permitted to observe the formation adducts a significantly weakened NSac···Br bonding interaction respect NBrSac strong Br···NPy interaction. topological properties at NSac···Br···NPy critical points (BCPs) frozen experimental geometries indicate increasing strength studied along series PyCN < PyCF3 PyCO2Me PyMe, correlating structural distances deeper negative molecular electrostatic potential values in individual molecules. polarizability calculated molecules clearly out atomic dipole moments NSac, Br, NPy atoms, magnitude within demonstrating their sensitivity external electric fields mimicking environments. In order explore effect polarizing environments on motif, an field applied (−40 × 10–4 ε 100 a.u.) extracted from all atoms except which optimized function ε. It shown that effective ranging 1.28 2.96 GV m–1 is necessary recover position Br-atom (from gas-phase optimization), providing evaluation crystalline environment. At any investigated geometry (i.e., full range fields), exhibit significant covalence degree both acceptor sides (measured by 1 |V|/G 2), addition nonnegligible delocalization index (DI(NSac|NPy)) 0.085–0.099. These features should be considered unique entity rather than two while pointing assembly small but contribution three-center four-electrons formal border atom transfer between moieties established magnitudes ρ BCPs, well DI, balance almost simultaneously regions. adduct straightforwardly driven polarization induced ε, permitting control variation moment adducts.