Inclusion properties of the clathrate crystals, (1)(C6H6) and (1)2(hydroquinone)(C6H6), derived from a conformationally flexible host compound 1-(9-anthryloxy)anthraquinone (1), have been investigated by means of X-ray crystallography, DSC analysis and 2H NMR spectroscopy. Complex (1)(C6H6) is a true clathrate: benzene is embedded in a host lattice constituted of the intermolecular face-to-face π–π overlap (π–π; 3.54 A) of the anthraquinone rings of 1. Crystal data: P21/c, a= 16.882(2), b= 8.970(1), c= 16.405(2)A, β= 91.53(2)°, Z= 4, Dc= 1.280 g cm–3. The crystal structure of a three-component clathrate (1)2(hydroquinone)(C6H6) shows the rigid two-component host lattice composed of 1 and hydroquinone. Crystal data: Pl, a= 11.779(3), b= 12.747(2), c= 8.818(1)A, α= 107.14(1), β= 92.59(3), γ= 101.86(3)°, Z= l, Dc= 1.335 g cm–3. The two host components are linked by the hydrogen bonds (O–O; 2.908, 2.912 A) as well as the unique orthogonal C–H–π–H–C (C–π; 3.2 A) and face-to-face π–π interactions (π–π; 3.43 A). Benzene is retained within the host lattice up to 173 °C. The crystal structure of guest-free host 1 has also been determined. Crystal data: P1, a= 15.566(5), b= 15.625(5), c= 11.571(2)A, α= 98.21(2), β= 94.20(2), γ= 132.74(2)°, Z= 4, Dc= 1.337 g cm –3. 2H NMR spectroscopy has been used to study the molecular motion of [2H6]benzene in the clathrates. Quadrapole echo line shapes, measured as a function of temperature, could be accounted for in terms of an in-plane 60° jump about the major symmetry axis. The activation parameters for a 60° jump are 9.4 and 19 kJ mol–1 for (1)(C6D6) and (1)2(hydroquinone)(C6D6), respectively.