Halogen‐substituted benzylamine crown ether inclusion complexes.

Noncovalent interactions have received much attention in the fields of supramolecular chemistry and crystal engineering. Hydrogen bonding and weak interaction forces affect crystal stacking. Crown‐ether‐based host–guest inclusion compounds with hydrogen bonding and weak intermolecular interaction forces deserve our attention. In addition, Xiong and co‐workers have proposed a molecular design strategy of H/F substitution. Based on this H/F substitution strategy, it is possible to develop halogen substitution, also known as the halogenation effect. Here, using benzylamine as an organic parent, the molecular design strategy of the halogenation effect was used. That is, halogen atoms (F, Cl, Br and I) were used to replace H atoms at the para site of the aromatic ring, and four halogenated benzylamine compounds were obtained, namely, 4‐fluorobenzylaminium di(methanesulfonyl)amidate–18‐crown‐6 (1/1), C7H9FN+·C2H6NO4S2−·C12H24O6 or [(4‐FBA)(18‐crown‐6)][DMSA], 1; 4‐chlorobenzylaminium di(methanesulfonyl)amidate–18‐crown‐6 (1/1), C7H9ClN+·C2H6NO4S2−·C12H24O6 or [(4‐ClBA)(18‐crown‐6)][DMSA], 2; 4‐bromobenzylaminium di(methanesulfonyl)amidate–18‐crown‐6 (1/1), C7H9BrN+·C2H6NO4S2−·C12H24O6 or [(4‐BrBA)(18‐crown‐6)][DMSA], 3; and 4‐iodobenzylaminium di(methanesulfonyl)amidate–18‐crown‐6 (1/1), C7H9IN+·C2H6NO4S2−·C12H24O6 or [(4‐IBA)(18‐crown‐6)][DMSA], 4. Clathrate 1 crystallizes in the space group P21, while 2–4 crystallize in the space group P21/n. In these compounds, extensive intermolecular interactions have been utilized for the self‐assembly of diverse supramolecular architectures. [ABSTRACT FROM AUTHOR]