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Background  The crystal structure of 2,2-trimethylenedioxy-4,4,6,6-tetrachlorocyclo triphosphazene has been determined at 120, 274 and 293 K. The result at 293 K confirms the room temperature  Cmc2  1  structure, but at the lower temperatures the space group is  Pna2  1 . Nevertheless the basic structure remains the same, with only small displacements of the atoms, amounting to an average of 25 pm between 120 and 293 K.    Results  X-ray diffraction and DSC results indicate that the phase transition takes place in two steps between 274 – 293 K and provides an understanding of previous NQR results. In the intermediate temperature range the molecules are displaced from their room temperature positions in such a way as to give an average structure with  Cmc2  1  symmetry.    Conclusion  The overall phase transition is consistent with the occurrence of a soft lattice mode at room temperature in which a large displacement of the molecule in the  x -direction is coupled with a flexing motion about an axis defined by the nitrogen atoms in the N1 and N3 positions.

Characterisation of temperature-dependent phase transitions in 2,2-trimethylenedioxy- 4,4,6,6-tetrachlorocyclotriphosphazene, N3P3Cl4[O(CH2)3O]