Pentachloro[alpha,alpha’,alpha(")-H-2(3)]toluene was studied by deuterium nuclear magnetic resonance (NMR) experiments. Three doublers were observed below 230 K, while a single doublet was observed above 300 K in a single crystal with its long axis perpendicular to the static magnetic field. The three doublers are attributable to the three disordered orientations of the molecule around its pseudo-6-fold axis, Populations in these three orientations were determined from the area intensities of the doublers. Below 150 K, the populations were found to be temperature-independent, indicating that the reorientational motions around the pseudo-6-fold axis are frozen into orientational disorder around this temperature and that the system is brought into a glassy crystalline state. A Hadamard quadrupole-order exchange NMR experiment was developed to determine the rates of the pseudo-6-fold reorientations by one-dimensional NMR, The cross and diagonal peak intensities of the exchange NMR spectra between 170 and 212 K were fitted well by using the three reorientation rates. A distribution of reorientation rates, which is often assumed in glassy materials, was not found. The temperature dependence of the reorientation rates could be described by Arrhenius law.