We have synthesized 3-t-butylchrysene and measured the Larmor frequency omega/2pi (= 8.50, 22.5, and 53.0 MHz) and temperature T (110-310 K) dependence of the proton spin-lattice relaxation rate R in the polycrystalline solid [low-frequency solid state nuclear magnetic resonance (NMR) relaxometry]. We have also determined the molecular and crystal structure in a single crystal of 3-t-butylchrysene using x-ray diffraction, which indicates the presence of a unique t-butyl group environment. The spin-1/2 protons relax as a result of the spin-spin dipolar interactions being modulated by the superimposed reorientation of the t-butyl groups and their constituent methyl groups. The reorientation is successfully modeled by the simplest motion; that of random hopping describable by Poisson statistics. The x-ray data indicate near mirror-plane symmetry that places one methyl group nearly in the aromatic plane and the other two almost equally above and below the plane. The NMR relaxometry data indicate that the nearly in-plane methyl group and the entire t-butyl group reorient with a barrier of 24.2 +/- 0.9 kJ mol(-1), and the two out-of-plane methyl groups reorient with a barrier of 14.2 +/- 0.6 kJ mol(-1). Following a brief review of methyl group rotation in simple ethyl-, and isopropyl-substituted one- and two-ring aromatic van der Waals molecular solids, the barriers for the out-of-plane methyl groups and the t-butyl group in 3-t-butylchrysene are compared with those barriers in three related molecular solids whose crystal structure is known: 4-methyl-2,6-di-t-butylphenol, 1,4-di-t-butylbenzene, and polymorph A of 2,6-di-t-butyl- naphthalene. A trend is observed in the reorientational barriers for the t-butyl and the out-of-plane methyl groups across this series of four compounds: as the t-butyl barriers decrease, the out-of-plane methyl barriers increase. (C) 2003 American Institute of Physics.