The 1H NMR spectra with the 13C satellites and the '3C spectra of 2-chloro- and 2-bromothiophene in nematic Merck ZLI 1167 and ZLI 1132 liquid crystal solutions were recorded and analyzed. The 'H spectra and three of the four 13C-satellite spectra appeared to be deceptively simple and prevented the determinations of certain individual coupling constants. As a consequence, the problems became under-determined. However, the use of two liquid crystal solvents and the assumption of unchanged structures in the solutions made it possible to determine the complete r α r α structures, although the linear dependence of some dipolar coupling constants led to more poorly determined groups of equations than was expected. The CH and CC distances, bond angles, and orientation matrix elements are reported for both 2-chloro- and 2-bromothiophene.