Abstract: | (2S*,4R*)‐2‐exo‐(1‐Naphthyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C20H17NO, (I), crystallizes with Z′ = 2 in the space group P21; the two independent molecules have the same absolute configuration, although this configuration is indeterminate. The molecules of each type are linked by a combination of C—H...O and C—H...π(arene) hydrogen bonds to form two independent sheets, each containing only one type of molecule. (2SR,4RS)‐7‐Methyl‐2‐exo‐(1‐naphthyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C21H19NO, (II), crystallizes as a true racemate in the space group P21/c, and a combination of C—H...N, C—H...O and C—H...π(arene) hydrogen bonds links the molecules into sheets, each containing equal numbers of the two enantiomorphs. (2S*,4R*)‐2‐exo‐(1‐Naphthyl)‐7‐trifluoromethyl‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C21H16F3NO2, (III), crystallizes as a single enantiomorph, as for (I), but now with Z′ = 1 in the space group P212121; again, the absolute configuration is indeterminate. A single C—H...π(arene) hydrogen bond links the molecules of (III) into simple chains. (2S,4R)‐8‐Chloro‐9‐methyl‐2‐exo‐(1‐naphthyl)‐2,3,4,5‐tetrahydro‐1H‐1,4‐epoxy‐1‐benzazepine, C21H18ClNO, (IV), crystallizes as a single enantiomorph of well defined configuration, in the space group P212121, where two independent C—H...π(arene) hydrogen bonds link the molecules into a single three‐dimensional framework structure. |