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Structural and motional features of C 60 .4C 6 H 6 solvate has been investigated by high-resolution 13 C solid-state NMR spectroscopy. 13 C line shape analysis of the cross-polarization spectrum for the static sample at 293 K shows an unusual motional restriction of benzene molecules in this solvate. The existence of highly anisotropic motion of benzene fraction is visualized also by the detection of important homo and heteronuclear dipolar interactions. 13 C magic-angle spinning spectra reveal a complex character of the C 60 NMR signal composed of three components with slightly different isotropic chemical shifts indicating the existence of magnetically nonequivalent positions or sites.