DOE OSTI2020
Na4Ni2C4SO16 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are eight inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with two NaO6 octahedra, edges with two NiO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 62–82°. There are a spread of Na–O bond distances ranging from 2.39–2.47 Å. In the second Na1+ site, Na1+ is bonded in a distorted hexagonal planar geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.36–2.48 Å. In the third Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with three NaO6 octahedra, edges with two NiO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 56–87°. There are a spread of Na–O bond distances ranging from 2.36–2.51 Å. In the fourth Na1+ site, Na1+ is bonded in a distorted hexagonal planar geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.38–2.53 Å. In the fifth Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with three NaO6 octahedra, edges with two NiO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 59–81°. There are a spread of Na–O bond distances ranging from 2.35–2.56 Å. In the sixth Na1+ site, Na1+ is bonded in a distorted hexagonal planar geometry to six O2- atoms. There are a spread of Na–O bond distances ranging from 2.38–2.50 Å. In the seventh Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with two NaO6 octahedra, edges with two NiO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 56–81°. There are a spread of Na–O bond distances ranging from 2.38–2.49 Å. In the eighth Na1+ site, Na1+ is bonded to six O2- atoms to form distorted NaO6 octahedra that share corners with two NaO6 octahedra, edges with two NiO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 59–87°. There are a spread of Na–O bond distances ranging from 2.39–2.48 Å. There are four inequivalent Ni3+ sites. In the first Ni3+ site, Ni3+ is bonded to six O2- atoms to form NiO6 octahedra that share edges with three NaO6 octahedra. There are a spread of Ni–O bond distances ranging from 2.06–2.12 Å. In the second Ni3+ site, Ni3+ is bonded to six O2- atoms to form NiO6 octahedra that share an edgeedge with one NaO6 octahedra. There are a spread of Ni–O bond distances ranging from 2.05–2.10 Å. In the third Ni3+ site, Ni3+ is bonded to six O2- atoms to form NiO6 octahedra that share edges with four NaO6 octahedra. There are a spread of Ni–O bond distances ranging from 2.06–2.11 Å. In the fourth Ni3+ site, Ni3+ is bonded to six O2- atoms to form NiO6 octahedra that share edges with two NaO6 octahedra. There are a spread of Ni–O bond distances ranging from 2.07–2.11 Å. There are eight inequivalent C4+ sites. In the first C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.29 Å) and one longer (1.30 Å) C–O bond length. In the second C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of C–O bond distances ranging from 1.28–1.30 Å. In the third C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.29 Å) and one longer (1.30 Å) C–O bond length. In the fourth C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is one shorter (1.29 Å) and two longer (1.30 Å) C–O bond length. In the fifth C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.29 Å) and one longer (1.30 Å) C–O bond length. In the sixth C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of C–O bond distances ranging from 1.28–1.30 Å. In the seventh C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of C–O bond distances ranging from 1.28–1.30 Å. In the eighth C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is one shorter (1.28 Å) and two longer (1.30 Å) C–O bond length. There are two inequivalent S6+ sites. In the first S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share edges with three NaO6 octahedra. There is two shorter (1.49 Å) and two longer (1.51 Å) S–O bond length. In the second S6+ site, S6+ is bonded to four O2- atoms to form SO4 tetrahedra that share edges with two NaO6 octahedra. There is two shorter (1.49 Å) and two longer (1.50 Å) S–O bond length. There are thirty-two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one S6+ atom. In the second O2- site, O2- is bonded to three Na1+ and one S6+ atom to form distorted edge-sharing ONa3S trigonal pyramids. In the third O2- site, O2- is bonded to three Na1+ and one S6+ atom to form distorted edge-sharing ONa3S trigonal pyramids. 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 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the seventh O2- site, O2- is bonded in a 4-coordinate geometry to two Na1+, one Ni3+, and one C4+ atom. In the eighth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the ninth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the tenth O2- site, O2- is bonded in a 1-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the eleventh O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the twelfth O2- site, O2- is bonded in a 1-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the thirteenth O2- site, O2- is bonded in a 4-coordinate geometry to two Na1+, one Ni3+, and one C4+ atom. In the fourteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Na1+, one Ni3+, and one C4+ atom. In the fifteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the sixteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Na1+, one Ni3+, and one C4+ atom. In the seventeenth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the eighteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the nineteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Na1+, one Ni3+, and one C4+ atom. In the twentieth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Na1+, one Ni3+, and one C4+ atom. In the twenty-first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Ni3+ and one C4+ atom. In the twenty-second O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the twenty-third O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the twenty-fourth O2- site, O2- is bonded in a 4-coordinate geometry to two Na1+, one Ni3+, and one C4+ atom. In the twenty-fifth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the twenty-sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Na1+, one Ni3+, and one C4+ atom. In the twenty-seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Na1+, one Ni3+, and one C4+ atom. In the twenty-eighth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to two Na1+, one Ni3+, and one C4+ atom. In the twenty-ninth O2- site, O2- is bonded in a 3-coordinate geometry to two Na1+ and one S6+ atom. In the thirtieth O2- site, O2- is bonded in a 1-coordinate geometry to two Na1+ and one S6+ atom. In the thirty-first O2- site, O2- is bonded in a distorted L-shaped geometry to one Na1+ and one S6+ atom. In the thirty-second O2- site, O2- is bonded in a distorted L-shaped geometry to one Na1+ and one S6+ atom.