A detailed comparison between molecular dynamics computer simulations and the experimental characterization of molecular motion through deuterium nuclear magnetic resonance (NMR) spectroscopic methods has been carried out for the crystalline phase of nylon 66 (polyhexamethyleneadipamide) at room temperature and just below the melting point. The computer simulations agree quantitatively with the experimental results at room temperature and qualitatively near the crystalline melting point. Both methods demonstrate that individual methylene groups within the crystals exhibit librational motion, which becomes very large in amplitude near the melting point, rather than undergoing discrete conformational jumps; furthermore, the hydrogen-bonded amides are relatively immobile at all temperatures below 230 degrees Celsius. The simulations are shown to be particularly useful for exaning the cooperativity of motion and for providing insight into structural-dynamical correlations. These aspects of the simulations are exemplified by the observation of concerted counterrotation of odd-numbered bonds within the methylene segments and the entropic stabilization of the crystal structure.