Ring conformations and intermolecular interactions in two fused dibenzoazocines

5‐Acetyl‐2‐chloro‐8,11‐dimethyl‐5,6,11,12‐tetrahydrodibenzo[b,f]azocine, C₁₉H₂₀ClNO, (I), crystallizes as a single fully ordered isomer, but 14‐acetyl‐8,11‐dimethyl‐7,8,13,14‐tetrahydrobenzo[f]naphtho[1,2‐b]azocine–14‐acetyl‐8,9‐dimethyl‐7,8,13,14‐tetrahydrobenzo[f]naphtho[1,2‐b]azocine (74/26), C₂₃H₂₃NO, (II), exhibits threefold whole‐molecule disorder involving both configurational and structural isomers. In (I) and in the predominant form of (II), the azocine rings adopt very similar conformations, forming boat‐shaped rings having approximate twofold rotational symmetry. There are no direction‐specific intermolecular interactions in the crystal structure of (I), but the molecules of (II) are weakly linked into chains by an aromatic π–π stacking interaction. The compounds were made under green conditions using an acid‐catalysed cyclization process having very high atom utilization.