F-19 single-quantum (SQC) and F-19-S-33 heteronuclear multiple-quantum coherence (HMQC) NMR spectroscopy of sulfur hexafluoride (SF6) dissolved in thermotropic liquid crystals (TLCs) were used to investigate the properties of TLCs. On one hand, environmental effects on the NMR parameters of SF6, F-19 nuclear shielding, F-19-S-33 spin-spin coupling, secondary isotope effects of sulfur on F-19 shielding, and the self-diffusion coefficient in the direction of the external magnetic field were studied as well. The temperature dependence of the F-19 shielding of SF6 in TLCs was modeled with a function that takes into account the properties of both TLC and SF6. It appears that the TLC environment deforms the electronic system of SF6 so that the F-19 shielding tensor becomes slightly anisotropic, with the anisotropy being from -0.5 to -1.4 ppm, depending upon the TLC solvent. On the contrary, no sign of residual dipolar coupling between F-19 and S-33 was found, meaning that the so-called deformational effects, which arise from the interaction between vibrational and reorientational motions of the molecule, on the geometry of the molecule are insignificant. Diffusion activation energies, Ea, were determined from the temperature dependence of the self-diffusion coefficients. In each TLC, Ea increases when moving from an isotropic phase to a nematic phase. The spin-spin coupling constant, J(F-19, S-33), increases by ca. 10 Hz when moving from the gas phase to TLC solutions. The secondary isotope shifts of F-19 shielding are practically independent of TLC solvent and temperature. For the first time, F-19-S-33 heteronuclear multiple-quantum NMR spectra were recorded for SF6 in the gas phase and in a liquid-crystalline solution.