An efficient and green procedure for the synthesis of novel 12‐aryl‐8,9,10,12‐tetrahydrobenzo[a]xanthen‐11‐one derivatives has been described through one‐pot condensation of 2‐naphthol, arylaldehyde and 5,5‐dimethyl‐cyclohexane‐1,3‐dione in the presence of sulfamic acid (NH2SO3H) in ionic liquid 1‐n‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIM]BF4). These reactions proceed with good yields under short reaction time. Furthermore, the green catalytic system can be recycled specific times with no decreases in yields and reaction rates.

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The asymmetric unit of the title compound, C13H20NO+·PF6 −, contains two cations, one complete anion and two half hexa­fluoro­phosphate anions having crystallographically imposed twofold rotation symmetry. In the cations, the morpholine rings are in a chair conformation. In the crystal, ions are linked by weak C—H⋯F hydrogen bonds into a three-dimensional network.