According to single crystal X-ray diffraction, neutron powder diffraction, solid state MAS NMR data, and differential scanning calorimetry, XeF 6 exists in at least six different modifications. Three of them are formed at temperatures above room temperature, one exists at room temperature, while two have been found at low temperatures. In the high temperature modifications XeF 6 forms a non-symmetric tetramer, better described as a cyclic trimer with a weakly associated monomer. The normal temperature modification is the previously described cubic phase IV, having disordered tetrameric and hexameric units. The low temperature modifications are regular tetramers. Only in presence of HF symmetric dimers are formed.