We investigate the relationship between intramolecular rotational dynamics and molecular and crystal structure in 4,4'-dimethoxyoctafluorobiphenyl. The techniques are electronic structure calculations, X-ray diffractometry, and H-1 and F-19 solid state nuclear magnetic resonance relaxation. We compute and measure barriers for coupled methyl group rotation and methoxy group libration. We compare the structure and the structure-motion relationship in 4,4'-dimethoxyoctafluorobiphenyl with the structure and the structure-motion relationship in related compounds in order to observe trends concerning the competition between intramolecular and intermolecular interactions. The H-1 spin lattice relaxation is nonexponential in both the high-temperature short-correlation time limit and in the low-temperature long-correlation time limit, albeit for different reasons. temperatures and it is exponential at high temperatures. The F-19 spin lattice relaxation is nonexponential at low temperatures and it is exponential at high temperatures.