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The crystal structures of meta -halogenated anilines 3-chloro- and 3-bromaniline have been determined for the first time. The crystal structure 3-iodoanoiline was re-determined with a sufficient quality using single-crystal X-ray diffraction. All three structures were analyzed from both geometric and energetic perspectives. Geometric analysis reveals common motifs such as zig-zag chains, bifurcated halogen bonds, and the dual donor–acceptor role of amino groups in hydrogen bonding. An energy-based approach, utilizing quantum chemical calculations, enables identification of the dominant interactions and basic structural motifs. While 3-chloroaniline forms columnar structures dominated by N–H···N and C–H···π interactions, the bromo- and iodo-analogs exhibit isostructural columnar-layered packing motives governed by stronger halogen bonding and π-type interactions. This combined approach emphasizes the importance of energy analysis in distinguishing structural hierarchies in systems with multiple weak interactions.
Konovalova et al. (Sat,) studied this question.