DOE OSTI2020
Na13Ca7S12(O16F)3 crystallizes in the monoclinic Pm space group. The structure is three-dimensional. there are nine inequivalent Na sites. In the first Na site, Na is bonded to six O atoms to form distorted NaO6 pentagonal pyramids that share corners with four CaO6F pentagonal bipyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Na–O bond distances ranging from 2.31–2.60 Å. In the second Na site, Na is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of Na–O bond distances ranging from 2.46–2.94 Å. In the third Na site, Na is bonded to six O and one F atom to form distorted NaO6F pentagonal bipyramids that share corners with four CaO6F pentagonal bipyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Na–O bond distances ranging from 2.42–2.71 Å. The Na–F bond length is 2.51 Å. In the fourth Na site, Na is bonded to six O atoms to form distorted NaO6 pentagonal pyramids that share corners with four CaO6F pentagonal bipyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Na–O bond distances ranging from 2.27–2.61 Å. In the fifth Na site, Na is bonded to six O atoms to form distorted NaO6 pentagonal pyramids that share corners with four CaO6F pentagonal bipyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Na–O bond distances ranging from 2.30–2.58 Å. In the sixth Na site, Na is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of Na–O bond distances ranging from 2.48–2.98 Å. In the seventh Na site, Na is bonded in a 9-coordinate geometry to nine O atoms. There are a spread of Na–O bond distances ranging from 2.42–2.97 Å. In the eighth Na site, Na is bonded to six O and one F atom to form distorted NaO6F pentagonal bipyramids that share corners with five CaO6F pentagonal bipyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Na–O bond distances ranging from 2.43–2.64 Å. The Na–F bond length is 2.55 Å. In the ninth Na site, Na is bonded in a 6-coordinate geometry to six O atoms. There are a spread of Na–O bond distances ranging from 2.48–2.57 Å. There are seven inequivalent Ca sites. In the first Ca site, Ca is bonded to six O and one F atom to form distorted CaO6F pentagonal bipyramids that share corners with two equivalent CaO6F pentagonal bipyramids, corners with three NaO6F pentagonal bipyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.40–2.56 Å. The Ca–F bond length is 2.24 Å. In the second Ca site, Ca is bonded in a 7-coordinate geometry to six O and one F atom. There are a spread of Ca–O bond distances ranging from 2.44–2.62 Å. The Ca–F bond length is 2.25 Å. In the third Ca site, Ca is bonded to six O and one F atom to form distorted CaO6F pentagonal bipyramids that share corners with two CaO6F pentagonal bipyramids, corners with four NaO6 pentagonal pyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.39–2.58 Å. The Ca–F bond length is 2.34 Å. In the fourth Ca site, Ca is bonded to six O and one F atom to form distorted CaO6F pentagonal bipyramids that share corners with two CaO6F pentagonal bipyramids, corners with four NaO6 pentagonal pyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.38–2.57 Å. The Ca–F bond length is 2.33 Å. In the fifth Ca site, Ca is bonded to six O and one F atom to form distorted CaO6F pentagonal bipyramids that share corners with three NaO6F pentagonal bipyramids, corners with three CaO6F pentagonal bipyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.44–2.66 Å. The Ca–F bond length is 2.24 Å. In the sixth Ca site, Ca is bonded to six O and one F atom to form distorted CaO6F pentagonal bipyramids that share a cornercorner with one CaO6F pentagonal bipyramid, corners with three NaO6F pentagonal bipyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.38–2.58 Å. The Ca–F bond length is 2.24 Å. In the seventh Ca site, Ca is bonded to six O and one F atom to form distorted CaO6F pentagonal bipyramids that share corners with two CaO6F pentagonal bipyramids, corners with four NaO6 pentagonal pyramids, corners with four SO4 tetrahedra, and an edgeedge with one SO4 tetrahedra. There are a spread of Ca–O bond distances ranging from 2.37–2.60 Å. The Ca–F bond length is 2.34 Å. There are twelve inequivalent S sites. In the first S site, S is bonded to four O atoms to form SO4 tetrahedra that share corners with four CaO6F pentagonal bipyramids and an edgeedge with one NaO6F pentagonal bipyramid. All S–O bond lengths are 1.49 Å. In the second S site, S is bonded to four O atoms to form SO4 tetrahedra that share corners with two CaO6F pentagonal bipyramids, corners with two equivalent NaO6 pentagonal pyramids, and an edgeedge with one CaO6F pentagonal bipyramid. All S–O bond lengths are 1.49 Å. In the third S site, S is bonded to four O atoms to form SO4 tetrahedra that share a cornercorner with one CaO6F pentagonal bipyramid, corners with two equivalent NaO6F pentagonal bipyramids, and a cornercorner with one NaO6 pentagonal pyramid. There are a spread of S–O bond distances ranging from 1.48–1.50 Å. In the fourth S site, S is bonded to four O atoms to form SO4 tetrahedra that share a cornercorner with one NaO6F pentagonal bipyramid, a cornercorner with one CaO6F pentagonal bipyramid, corners with two equivalent NaO6 pentagonal pyramids, and an edgeedge with one CaO6F pentagonal bipyramid. There are a spread of S–O bond distances ranging from 1.48–1.50 Å. In the fifth S site, S is bonded to four O atoms to form SO4 tetrahedra that share corners with two CaO6F pentagonal bipyramids, corners with two equivalent NaO6 pentagonal pyramids, and an edgeedge with one CaO6F pentagonal bipyramid. All S–O bond lengths are 1.49 Å. In the sixth S site, S is bonded to four O atoms to form SO4 tetrahedra that share a cornercorner with one NaO6F pentagonal bipyramid, a cornercorner with one CaO6F pentagonal bipyramid, and an edgeedge with one CaO6F pentagonal bipyramid. There are a spread of S–O bond distances ranging from 1.47–1.50 Å. In the seventh S site, S is bonded to four O atoms to form SO4 tetrahedra that share a cornercorner with one NaO6F pentagonal bipyramid, corners with two equivalent CaO6F pentagonal bipyramids, and an edgeedge with one CaO6F pentagonal bipyramid. There are a spread of S–O bond distances ranging from 1.47–1.50 Å. In the eighth S site, S is bonded to four O atoms to form SO4 tetrahedra that share corners with three CaO6F pentagonal bipyramids, a cornercorner with one NaO6 pentagonal pyramid, and an edgeedge with one NaO6 pentagonal pyramid. There is three shorter (1.49 Å) and one longer (1.50 Å) S–O bond length. In the ninth S site, S is bonded to four O atoms to form SO4 tetrahedra that share a cornercorner with one NaO6F pentagonal bipyramid, corners with two equivalent CaO6F pentagonal bipyramids, a cornercorner with one NaO6 pentagonal pyramid, and an edgeedge with one NaO6 pentagonal pyramid. There is two shorter (1.49 Å) and two longer (1.50 Å) S–O bond length. In the tenth S site, S is bonded to four O atoms to form SO4 tetrahedra that share corners with two equivalent NaO6F pentagonal bipyramids, corners with two CaO6F pentagonal bipyramids, and an edgeedge with one CaO6F pentagonal bipyramid. All S–O bond lengths are 1.49 Å. In the eleventh S site, S is bonded to four O atoms to form SO4 tetrahedra that share corners with two equivalent CaO6F pentagonal bipyramids, corners with two NaO6 pentagonal pyramids, and an edgeedge with one NaO6 pentagonal pyramid. There is two shorter (1.49 Å) and two longer (1.50 Å) S–O bond length. In the twelfth S site, S is bonded to four O atoms to form SO4 tetrahedra that share corners with two equivalent CaO6F pentagonal bipyramids, a cornercorner with one NaO6 pentagonal pyramid, and an edgeedge with one NaO6F pentagonal bipyramid. There are a spread of S–O bond distances ranging from 1.48–1.50 Å. There are thirty-six inequivalent O sites. In the first O site, O is bonded in a 1-coordinate geometry to two Na, one Ca, and one S atom. In the second O site, O is bonded in a distorted rectangular see-saw-like geometry to three Na and one S atom. In the third O site, O is bonded in a 4-coordinate geometry to two equivalent Na, one Ca, and one S atom. In the fourth O site, O is bonded in a 1-coordinate geometry to two Na, one Ca, and one S atom. In the fifth O site, O is bonded in a 4-coordinate geometry to two equivalent Na, one Ca, and one S atom. In the sixth O site, O is bonded to two equivalent Na, one Ca, and one S atom to form distorted corner-sharing ONa2CaS tetrahedra. In the seventh O site, O is bonded in a 4-coordinate geometry to three Na and one S atom. In the eighth O site, O is bonded in a 4-coordinate geometry to three Na and one S atom. In the ninth O site, O is bonded in a 1-coordinate geometry to two Na, one Ca, and one S atom. In the tenth O site, O is bonded in a 1-coordinate geometry to two Na, one Ca, and one S atom. In the eleventh O site, O is bonded in a 1-coordinate geometry to one Na, two Ca, and one S atom. In the twelfth O site, O is bonded in a 4-coordinate geometry to two equivalent Na, one Ca, and one S atom. In the thirteenth O site, O is bonded in a 1-coordinate geometry to two equivalent Na, one Ca, and one S atom. In the fourteenth O site, O is bonded to three Na and one S atom to form distorted corner-sharing ONa3S tetrahedra. In the fifteenth O site, O is bonded in a 1-coordinate geometry to three Na and one S atom. In the sixteenth O site, O is bonded in a 1-coordinate geometry to two Na, one Ca, and one S atom. In the seventeenth O site, O is bonded to two equivalent Na, one Ca, and one S atom to form distorted corner-sharing ONa2CaS tetrahedra. In the eighteenth O site, O is bonded in a 1-coordinate geometry to two equivalent Na, one Ca, and one S atom. In the nineteenth O site, O is bonded in a 4-coordinate geometry to two equivalent Na, one Ca, and one S atom. In the twentieth O site, O is bonded in a 4-coordinate geometry to three Na and one S atom. In the twenty-first O site, O is bonded in a 1-coordinate geometry to two Na, one Ca, and one S atom. In the twenty-second O site, O is bonded in a 1-coordinate geometry to three Na and one S atom. In the twenty-third O site, O is bonded in a 4-coordinate geometry to two equivalent Na, one Ca, and one S atom. In the twenty-fourth O site, O is bonded in a 4-coordinate geometry to two equivalent Na, one Ca, and one S atom. In the twenty-fifth O site, O is bonded in a 4-coordinate geometry to two equivalent Na, one Ca, and one S atom. In the twenty-sixth O site, O is bonded in a 1-coordinate geometry to one Na, two Ca, and one S atom. In the twenty-seventh O site, O is bonded in a 1-coordinate geometry to one Na, one Ca, and one S atom. In the twenty-eighth O site, O is bonded in a 1-coordinate geometry to two Na, one Ca, and one S atom. In the twenty-ninth O site, O is bonded to three Na and one S atom to form distorted ONa3S tetrahedra that share corners with six ONa2CaS tetrahedra and edges with two ONa3S tetrahedra. In the thirtieth O site, O is bonded to two equivalent Na, one Ca, and one S atom to form distorted ONa2CaS tetrahedra that share corners with six ONa3S tetrahedra and edges with two ONa2CaS tetrahedra. In the thirty-first O site, O is bonded to two equivalent Na, one Ca, and one S atom to form distorted ONa2CaS tetrahe