Abstract: | The crystal structure of trisodium octafluoridotantalate, Na3TaF8, has been redetermined using diffractometer data collected at 153 K, resulting in more accurate bond distances and angles than obtained from a previous structure determination based on film data. The structure is built from layers running along 101], which are formed by distorted TaF8] antiprisms and NaF6] rectangular bipyramids sharing edges and corners. The individual layers are separated by eight‐coordinated Na ions. Two atoms in the asymmetric unit are in special positions: the Ta atom is on a twofold axis in Wyckoff position 4e and one of the Na ions lies on an inversion centre in Wyckoff site 4d. |