The crystal structure of H-ZSM-5 loaded with 3.68(2) molecules naphthalene per unit cell was solved by single crystal X-ray diffraction. The space group is orthorhombic, Pnma, with a = 19.919(1), b = 19.955(2) and c = 13.357(1) and V = 5309(1) 3 . There are eight Si 1 1 . 9 6 Al 0 . 0 4 O 2 4 0.46C 1 0 H 8 (+ 0.04H + ) units per unit cell. D x = 1.959 Mg m - 3 , λ(MoK α ) = 0.71069 and μ(MoK α ) = 0.677 mm - 1 . The finalR (R w ) = 0.044 (0.038),w = 1/σ 2 (F), for 5605 observed reflections with I > 2.0 σ(I) measured at 293 K. The inversion of the a and b unit cell parameters (a/b = 0.996), first reported by Mentzen et al. [B.F. Mentzen, M. Sacerdote-Peronnet, J.F. Berar and F. Lefebvre, Zeolites, 13 (1993) 485] is confirmed. The straight channel axis along [010] has elliptical cross-sections with limiting apertures of 4.55 6.44 (r o x y g e n = 1.35 ). The 10-ring pores in the sinusoidal channel remain almost circular (major and minor axes being about 5.6 and 5.2 ). Naphthalene molecules are located at the channel intersections. Their long molecular axis (parallel to a molecular 2-fold axis) deviates 1.7° from [010]. The angle between the normal on the plane of the molecule and the positive a axis is 40.5(3)°. The naphthalene molecules form loosely connected chains in the straight channel; the shortest non-bonding C-C distance between neighbouring molecules in the straight channel is 4.57(2) .