The determination of accurate structures of relatively small molecules dissolved in liquid-crystal solvents is no trivial matter. Extensive vibrational corrections to the observed dipolar couplings are required. Vibrational force fields are often available, but the usual harmonic corrections are strictly limited to small-amplitude internal motions. Moreover, the need to also apply anharmonic corrections and to include the elusive vibration reorientation interaction is problematic and can only be fulfilled for a very limited set of small molecules. In this paper we discuss the implications for the accuracy of the structure of larger molecules for which this information is not available. We discuss the examples of azulene and biphenylene, and set realistic limits on their proton structures, derived from H-1 dipolar couplings extracted from NMR spectra obtained in different liquid-crystal solvents and analyzed with sophisticated evolutionary algorithms.