Materials Data on Na6HfH8S5O24 by Materials Project
Na6HfH8S5O24 crystallizes in the monoclinic P2_1 space group. The structure is three-dimensional. there are six inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to six O2- atoms to form NaO6 octahedra that share corners with two equivalent NaO6 octahedra, corners with six SO4 tetrahedra, and an edgeedge with one NaO7 pentagonal bipyramid. The corner-sharing octahedra tilt angles range from 64–71°. There are a spread of Na–O bond distances ranging from 2.30–2.46 Å. In the second Na1+ site, Na1+ is bonded in a 5-coordinate geometry to seven O2- atoms. There are a spread of Na–O bond distances ranging from 2.32–2.97 Å. In the third Na1+ site, Na1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.32–2.87 Å. In the fourth Na1+ site, Na1+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Na–O bond distances ranging from 2.37–2.91 Å. In the fifth Na1+ site, Na1+ is bonded to seven O2- atoms to form distorted NaO7 pentagonal bipyramids that share a cornercorner with one NaO6 octahedra, corners with three SO4 tetrahedra, an edgeedge with one NaO6 octahedra, and edges with two SO4 tetrahedra. The corner-sharing octahedral tilt angles are 68°. There are a spread of Na–O bond distances ranging from 2.43–2.68 Å. In the sixth Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with two equivalent NaO6 octahedra, a cornercorner with one NaO7 pentagonal bipyramid, corners with three SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 64–71°. There are a spread of Na–O bond distances ranging from 2.38–2.70 Å. Hf4+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Hf–O bond distances ranging from 2.10–2.32 Å. There are eight inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the second H1+ site, H1+ is bonded in a distorted single-bond geometry to two O2- atoms. There is one shorter (1.01 Å) and one longer (1.65 Å) H–O bond length. In the third H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the seventh H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the eighth H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. There are five inequivalent S6+ sites. In the first S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with two NaO6 octahedra and a cornercorner with one NaO7 pentagonal bipyramid. The corner-sharing octahedra tilt angles range from 52–53°. There are a spread of S–O bond distances ranging from 1.47–1.53 Å. In the second S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with two NaO6 octahedra and a cornercorner with one NaO7 pentagonal bipyramid. The corner-sharing octahedra tilt angles range from 45–61°. There are a spread of S–O bond distances ranging from 1.47–1.54 Å. In the third S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with two equivalent NaO6 octahedra, an edgeedge with one NaO6 octahedra, and an edgeedge with one NaO7 pentagonal bipyramid. The corner-sharing octahedra tilt angles range from 45–58°. There are a spread of S–O bond distances ranging from 1.48–1.52 Å. In the fourth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share corners with two equivalent NaO6 octahedra and an edgeedge with one NaO7 pentagonal bipyramid. The corner-sharing octahedra tilt angles range from 23–51°. There are a spread of S–O bond distances ranging from 1.46–1.53 Å. In the fifth S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share a cornercorner with one NaO6 octahedra and a cornercorner with one NaO7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 46°. There are a spread of S–O bond distances ranging from 1.46–1.54 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted water-like geometry to one Hf4+ and one S6+ atom. In the second O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Hf4+, and one S6+ atom. In the third O2- site, O2- is bonded in a distorted single-bond geometry to two Na1+ and one S6+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one S6+ atom. In the fifth O2- site, O2- is bonded in a bent 150 degrees geometry to one Hf4+ and one S6+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one S6+ atom. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one S6+ atom. In the eighth O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one S6+ atom. In the ninth O2- site, O2- is bonded in a bent 150 degrees geometry to one Hf4+ and one S6+ atom. In the tenth O2- site, O2- is bonded in a distorted tetrahedral geometry to three Na1+ and one S6+ atom. In the eleventh O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one S6+ atom. In the twelfth O2- site, O2- is bonded in a 1-coordinate geometry to two Na1+ and one S6+ atom. In the thirteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Hf4+, and one S6+ atom. In the fourteenth O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one S6+ atom. In the fifteenth O2- site, O2- is bonded in a 2-coordinate geometry to three Na1+, one H1+, and one S6+ atom. In the sixteenth O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one S6+ atom. In the seventeenth O2- site, O2- is bonded in a distorted water-like geometry to one Na1+, one Hf4+, and one S6+ atom. In the eighteenth O2- site, O2- is bonded in a 1-coordinate geometry to one Na1+, one Hf4+, and one S6+ atom. In the nineteenth O2- site, O2- is bonded in a 1-coordinate geometry to two Na1+ and one S6+ atom. In the twentieth O2- site, O2- is bonded in a 1-coordinate geometry to two Na1+ and one S6+ atom. In the twenty-first O2- site, O2- is bonded in a water-like geometry to one Na1+, one Hf4+, and two H1+ atoms. In the twenty-second O2- site, O2- is bonded in a distorted water-like geometry to two Na1+ and two H1+ atoms. In the twenty-third O2- site, O2- is bonded in a distorted water-like geometry to two Na1+ and two H1+ atoms. In the twenty-fourth O2- site, O2- is bonded in a distorted water-like geometry to two Na1+ and two H1+ atoms.