At higher pore fillings (n greater than or equal to 4) the silicalite(SIL)/nbenzene(BENZ) solid state phase diagram is very complex. The crystal structures of the 4, 6, and 8 molecules/uc loaded stoichiometric benzenates are investigated by X-ray powder diffraction profile refinements (Rietveld method) and energy minimization calculations (Buckingham model). In SIL.4BENZ (monoclinic P2(1)/n.1.1, M symmetry), the benzene molecule is disordered and presents at least two distinct orientations centred near the channel intersections (sites I). In SIL.6BENZ (orthorhombic P2(1)2(1)2(1), O2 symmetry), the two independent benzene molecules are located at the channel intersections (sites I) and in the zigzag channels (sites II); the benzene at site I might be disordered (several equi-probable orientations as in SIL.4BENZ). In the sorbate saturated SIL.8BENZ complex (orthorhombic Pnma, O1 symmetry) the two independent sorbate species are ordered and located at sites I and in the straight channels (sites III). In SIL.6BENZ and SIL.8BENZ, the sorbate/sorbate interactions are comparable to those observed in crystalline benzene (T-association). Sorption of benzene in the MFI channels provokes a strong elliptical deformation of the pore openings. At benzene saturation, the MFI unit-cell parameters correspond to a pseudo-tetragonal deformation, but the framework symmetry remains orthorhombic O1.