DOE OSTI2020
Na3SO4F crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. there are thirteen inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to four O2- and two equivalent F1- atoms to form NaO4F2 octahedra that share corners with four equivalent NaO4F2 octahedra, corners with four SO4 tetrahedra, and edges with two equivalent NaO4F2 octahedra. The corner-sharing octahedra tilt angles range from 8–89°. There are two shorter (2.38 Å) and two longer (2.52 Å) Na–O bond lengths. Both Na–F bond lengths are 2.37 Å. In the second Na1+ site, Na1+ is bonded in a 7-coordinate geometry to six O2- and two F1- atoms. There are a spread of Na–O bond distances ranging from 2.44–3.04 Å. There are one shorter (2.27 Å) and one longer (2.61 Å) Na–F bond lengths. In the third Na1+ site, Na1+ is bonded to four O2- and two F1- atoms to form distorted NaO4F2 octahedra that share corners with three NaO4F2 octahedra, corners with four SO4 tetrahedra, edges with four NaO4F2 octahedra, and faces with two equivalent NaO4F2 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 17–74°. There are two shorter (2.39 Å) and two longer (2.61 Å) Na–O bond lengths. There are one shorter (2.26 Å) and one longer (2.33 Å) Na–F bond lengths. In the fourth Na1+ site, Na1+ is bonded in a 6-coordinate geometry to four O2- and two F1- atoms. There are a spread of Na–O bond distances ranging from 2.42–2.54 Å. There are one shorter (2.35 Å) and one longer (2.39 Å) Na–F bond lengths. In the fifth Na1+ site, Na1+ is bonded to four O2- and two F1- atoms to form distorted NaO4F2 octahedra that share corners with three NaO4F2 octahedra, corners with four SO4 tetrahedra, edges with two equivalent NaO4F2 octahedra, and faces with two equivalent NaO4F2 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 17–77°. There are a spread of Na–O bond distances ranging from 2.39–2.52 Å. There are one shorter (2.35 Å) and one longer (2.41 Å) Na–F bond lengths. In the sixth Na1+ site, Na1+ is bonded in a 7-coordinate geometry to five O2- and two F1- atoms. There are a spread of Na–O bond distances ranging from 2.40–2.96 Å. There are one shorter (2.28 Å) and one longer (2.72 Å) Na–F bond lengths. In the seventh Na1+ site, Na1+ is bonded to four O2- and two equivalent F1- atoms to form distorted NaO4F2 octahedra that share corners with two equivalent NaO4F2 octahedra, corners with two equivalent NaO4F2 pentagonal pyramids, corners with four SO4 tetrahedra, edges with four NaO4F2 octahedra, and faces with two equivalent NaO4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles are 77°. There are two shorter (2.47 Å) and two longer (2.52 Å) Na–O bond lengths. Both Na–F bond lengths are 2.25 Å. In the eighth Na1+ site, Na1+ is bonded in a 6-coordinate geometry to four O2- and two F1- atoms. There are a spread of Na–O bond distances ranging from 2.36–2.47 Å. There are one shorter (2.32 Å) and one longer (2.63 Å) Na–F bond lengths. In the ninth Na1+ site, Na1+ is bonded to four O2- and two F1- atoms to form distorted NaO4F2 octahedra that share corners with four NaO4F2 octahedra, corners with four SO4 tetrahedra, edges with three NaO4F2 octahedra, and a faceface with one NaO4F2 octahedra. The corner-sharing octahedra tilt angles range from 12–77°. There are a spread of Na–O bond distances ranging from 2.34–2.48 Å. There are one shorter (2.34 Å) and one longer (2.44 Å) Na–F bond lengths. In the tenth Na1+ site, Na1+ is bonded to four O2- and two F1- atoms to form distorted NaO4F2 octahedra that share corners with three NaO4F2 octahedra, corners with four SO4 tetrahedra, edges with two NaO4F2 octahedra, and a faceface with one NaO4F2 octahedra. The corner-sharing octahedra tilt angles range from 8–89°. There are a spread of Na–O bond distances ranging from 2.41–2.58 Å. There are one shorter (2.33 Å) and one longer (2.48 Å) Na–F bond lengths. In the eleventh Na1+ site, Na1+ is bonded to four O2- and two F1- atoms to form NaO4F2 octahedra that share corners with two NaO4F2 octahedra, corners with four SO4 tetrahedra, and edges with three NaO4F2 octahedra. The corner-sharing octahedra tilt angles range from 20–74°. There are a spread of Na–O bond distances ranging from 2.41–2.51 Å. There are one shorter (2.35 Å) and one longer (2.36 Å) Na–F bond lengths. In the twelfth Na1+ site, Na1+ is bonded in a 7-coordinate geometry to four O2- and two F1- atoms. There are a spread of Na–O bond distances ranging from 2.40–2.72 Å. There are one shorter (2.37 Å) and one longer (2.41 Å) Na–F bond lengths. In the thirteenth Na1+ site, Na1+ is bonded to four O2- and two F1- atoms to form distorted NaO4F2 pentagonal pyramids that share a cornercorner with one NaO4F2 octahedra, a cornercorner with one NaO4F2 pentagonal pyramid, corners with four SO4 tetrahedra, faces with three NaO4F2 octahedra, and a faceface with one NaO4F2 pentagonal pyramid. The corner-sharing octahedral tilt angles are 11°. There are a spread of Na–O bond distances ranging from 2.39–2.48 Å. There are one shorter (2.34 Å) and one longer (2.47 Å) Na–F bond lengths. There are six inequivalent S6+ sites. In the first S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with seven NaO4F2 octahedra and corners with two equivalent NaO4F2 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 45–62°. There is three shorter (1.49 Å) and one longer (1.50 Å) S–O bond length. In the second S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with eight NaO4F2 octahedra. The corner-sharing octahedra tilt angles range from 51–60°. There is two shorter (1.49 Å) and two longer (1.50 Å) S–O bond length. In the third S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with seven NaO4F2 octahedra. The corner-sharing octahedra tilt angles range from 45–61°. There are a spread of S–O bond distances ranging from 1.48–1.50 Å. In the fourth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with three NaO4F2 octahedra and corners with four equivalent NaO4F2 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 53–56°. There is three shorter (1.49 Å) and one longer (1.50 Å) S–O bond length. In the fifth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with six NaO4F2 octahedra. The corner-sharing octahedra tilt angles range from 49–64°. There is one shorter (1.49 Å) and three longer (1.50 Å) S–O bond length. In the sixth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with nine NaO4F2 octahedra and corners with two equivalent NaO4F2 pentagonal pyramids. The corner-sharing octahedra tilt angles range from 51–65°. There is three shorter (1.49 Å) and one longer (1.50 Å) S–O bond length. There are eighteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one S6+ atom. In the second O2- site, O2- is bonded in a rectangular see-saw-like geometry to three Na1+ and one S6+ atom. In the third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a 4-coordinate geometry to three Na1+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a 1-coordinate geometry to four Na1+ and one S6+ atom. In the sixth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one S6+ atom. In the seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one S6+ atom. In the eighth O2- site, O2- is bonded in a 1-coordinate geometry to three Na1+ and one S6+ atom. In the ninth O2- site, O2- is bonded to three Na1+ and one S6+ atom to form distorted ONa3S tetrahedra that share corners with six FNa6 octahedra. The corner-sharing octahedra tilt angles range from 13–66°. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one S6+ atom. In the eleventh O2- site, O2- is bonded in a 1-coordinate geometry to three Na1+ and one S6+ atom. In the twelfth O2- site, O2- is bonded to three Na1+ and one S6+ atom to form distorted ONa3S tetrahedra that share corners with six FNa6 octahedra. The corner-sharing octahedra tilt angles range from 14–64°. In the thirteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one S6+ atom. In the fourteenth O2- site, O2- is bonded to three Na1+ and one S6+ atom to form distorted ONa3S tetrahedra that share corners with four FNa6 octahedra. The corner-sharing octahedra tilt angles range from 8–71°. In the fifteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to three Na1+ and one S6+ atom. In the sixteenth O2- site, O2- is bonded in a 1-coordinate geometry to four Na1+ and one S6+ atom. In the seventeenth O2- site, O2- is bonded in a 4-coordinate geometry to three Na1+ and one S6+ atom. In the eighteenth O2- site, O2- is bonded in a 1-coordinate geometry to three Na1+ and one S6+ atom. There are six inequivalent F1- sites. In the first F1- site, F1- is bonded to six Na1+ atoms to form FNa6 octahedra that share corners with three FNa6 octahedra, a cornercorner with one ONa3S tetrahedra, and a faceface with one FNa6 octahedra. The corner-sharing octahedra tilt angles range from 0–11°. In the second F1- site, F1- is bonded to six Na1+ atoms to form distorted FNa6 octahedra that share corners with three ONa3S tetrahedra and a faceface with one FNa6 octahedra. In the third F1- site, F1- is bonded in a 6-coordinate geometry to six Na1+ atoms. In the fourth F1- site, F1- is bonded to six Na1+ atoms to form distorted FNa6 octahedra that share corners with two equivalent FNa6 octahedra, corners with three ONa3S tetrahedra, and a faceface with one FNa6 octahedra. The corner-sharing octahedral tilt angles are 0°. In the fifth F1- site, F1- is bonded to six Na1+ atoms to form distorted FNa6 octahedra that share a cornercorner with one FNa6 octahedra, corners with three ONa3S tetrahedra, and a faceface with one FNa6 octahedra. The corner-sharing octahedral tilt angles are 11°. In the sixth F1- site, F1- is bonded to six Na1+ atoms to form FNa6 octahedra that share corners with six ONa3S tetrahedra and faces with two FNa6 octahedra.