Abstract: | In the structure of the complex of dibenzo‐18‐crown‐6 systematic name: 2,5,8,15,18,21‐hexaoxatricyclo20.4.0.09,14]hexacosa‐1(26),9,11,13,22,24‐hexaene] with 4‐methoxyanilinium tetrafluoroborate, C7H10NO+·BF4?·C20H24O6, the protonated 4‐methoxyanilinium (MB‐NH3+) cation forms a 1:1 supramolecular rotator–stator complex with the dibenzo‐18‐crown‐6 molecule via N—H...O hydrogen bonds. The MB‐NH3+ group is attached from the convex side of the bowl‐shaped crown, in contrast with similar ammonium cations that nest in the curvature of the bowl. The cations are associated via C—H...π interactions, while the cations and anions are linked by weak C—H...F hydrogen bonds, forming cation–crown–anion chains parallel to 011]. |