DOE OSTI2020
Li4Co2C4SO16 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are eight inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with four LiO6 octahedra, edges with two CoO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 56–84°. There are a spread of Li–O bond distances ranging from 2.18–2.29 Å. In the second Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.03–2.39 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with three LiO6 octahedra, edges with two CoO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 56–61°. There are a spread of Li–O bond distances ranging from 2.10–2.42 Å. In the fourth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with five LiO6 octahedra, edges with two CoO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 55–82°. There are a spread of Li–O bond distances ranging from 2.14–2.29 Å. In the fifth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with three LiO6 octahedra, edges with two CoO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 79–84°. There are a spread of Li–O bond distances ranging from 2.07–2.36 Å. In the sixth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with four LiO6 octahedra, edges with two CoO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 53–79°. There are a spread of Li–O bond distances ranging from 2.16–2.30 Å. In the seventh Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with three LiO6 octahedra, edges with two CoO6 octahedra, and an edgeedge with one SO4 tetrahedra. The corner-sharing octahedra tilt angles range from 53–65°. There are a spread of Li–O bond distances ranging from 2.10–2.46 Å. In the eighth Li1+ site, Li1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.04–2.32 Å. There are four inequivalent Co3+ sites. In the first Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share edges with three LiO6 octahedra. There are a spread of Co–O bond distances ranging from 1.93–1.98 Å. In the second Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share edges with two LiO6 octahedra. There are a spread of Co–O bond distances ranging from 1.93–1.95 Å. In the third Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share edges with three LiO6 octahedra. There are a spread of Co–O bond distances ranging from 1.91–1.95 Å. In the fourth Co3+ site, Co3+ is bonded to six O2- atoms to form CoO6 octahedra that share edges with four LiO6 octahedra. There are a spread of Co–O bond distances ranging from 1.93–1.98 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 are a spread of C–O bond distances ranging from 1.28–1.31 Å. 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 1.27–1.31 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 (1.28 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 (1.31 Å) C–O bond length. In the sixth 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 seventh 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 eighth 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 1.28–1.31 Å. 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 five LiO6 octahedra. There is two shorter (1.48 Å) and two 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 an edgeedge with one LiO6 octahedra. There is two shorter (1.48 Å) and two longer (1.51 Å) S–O bond length. There are thirty-two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Co3+, and one C4+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Co3+, and one C4+ atom. In the third O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Co3+, and one C4+ atom. In the fourth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Co3+, and one C4+ atom. In the fifth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Co3+, and one C4+ atom. In the sixth O2- site, O2- is bonded in a distorted T-shaped geometry to two Li1+ and one S6+ atom. In the seventh O2- site, O2- is bonded to three Li1+ and one S6+ atom to form distorted edge-sharing OLi3S trigonal pyramids. In the eighth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Co3+ and one C4+ atom. In the ninth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Co3+, and one C4+ atom. In the tenth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to one Li1+, one Co3+, and one C4+ atom. In the eleventh O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Co3+, and one C4+ atom. In the twelfth O2- site, O2- is bonded in a distorted T-shaped geometry to two Li1+ and one S6+ atom. In the thirteenth O2- site, O2- is bonded to three Li1+ and one S6+ atom to form distorted edge-sharing OLi3S trigonal pyramids. In the fourteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Co3+, and one C4+ atom. In the fifteenth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Co3+, and one C4+ atom. In the sixteenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Co3+, and one C4+ atom. In the seventeenth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Co3+, and one C4+ atom. In the eighteenth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Co3+, and one C4+ atom. In the nineteenth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Co3+, and one C4+ atom. In the twentieth O2- site, O2- is bonded in a distorted T-shaped geometry to two Li1+ and one S6+ atom. In the twenty-first O2- site, O2- is bonded in a distorted T-shaped geometry to two Li1+ and one S6+ atom. In the twenty-second O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Co3+, and one C4+ atom. In the twenty-third O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Co3+, and one C4+ atom. In the twenty-fourth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Co3+, and one C4+ atom. In the twenty-fifth O2- site, O2- is bonded in a 3-coordinate geometry to one Li1+, one Co3+, and one C4+ atom. In the twenty-sixth O2- site, O2- is bonded in an L-shaped geometry to one Li1+ and one S6+ atom. In the twenty-seventh O2- site, O2- is bonded in an L-shaped geometry to one Li1+ and one S6+ atom. In the twenty-eighth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Co3+, and one C4+ atom. In the twenty-ninth O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Co3+, and one C4+ atom. In the thirtieth O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Co3+, and one C4+ atom. In the thirty-first O2- site, O2- is bonded in a 4-coordinate geometry to two Li1+, one Co3+, and one C4+ atom. In the thirty-second O2- site, O2- is bonded in a distorted trigonal planar geometry to one Li1+, one Co3+, and one C4+ atom.