DOE OSTI2020
Li3Mn4O8 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are twelve inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.94–2.10 Å. In the second Li1+ site, Li1+ is bonded to five O2- atoms to form distorted LiO5 trigonal bipyramids that share corners with four MnO6 octahedra, corners with four MnO5 square pyramids, an edgeedge with one MnO5 square pyramid, edges with two equivalent LiO5 trigonal bipyramids, and a faceface with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 43–54°. There are a spread of Li–O bond distances ranging from 2.01–2.35 Å. In the third Li1+ site, Li1+ is bonded to five O2- atoms to form distorted LiO5 trigonal bipyramids that share corners with four MnO6 octahedra, corners with four MnO5 square pyramids, an edgeedge with one MnO5 square pyramid, edges with two equivalent LiO5 trigonal bipyramids, and a faceface with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 43–54°. There are a spread of Li–O bond distances ranging from 2.01–2.30 Å. In the fourth Li1+ site, Li1+ is bonded in a 1-coordinate geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.89–2.57 Å. In the fifth Li1+ site, Li1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 1.91–2.35 Å. In the sixth Li1+ site, Li1+ is bonded to five O2- atoms to form distorted LiO5 trigonal bipyramids that share corners with four MnO6 octahedra, corners with four MnO5 square pyramids, an edgeedge with one MnO5 square pyramid, and a faceface with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 38–57°. There are a spread of Li–O bond distances ranging from 2.01–2.24 Å. In the seventh Li1+ site, Li1+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Li–O bond distances ranging from 1.94–2.11 Å. In the eighth Li1+ site, Li1+ is bonded to five O2- atoms to form distorted LiO5 trigonal bipyramids that share corners with four MnO6 octahedra, corners with four MnO5 square pyramids, an edgeedge with one MnO5 square pyramid, edges with two equivalent LiO5 trigonal bipyramids, and a faceface with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 42–54°. There are a spread of Li–O bond distances ranging from 2.01–2.33 Å. In the ninth Li1+ site, Li1+ is bonded to five O2- atoms to form distorted LiO5 trigonal bipyramids that share corners with four MnO6 octahedra, corners with four MnO5 square pyramids, an edgeedge with one MnO5 square pyramid, edges with two equivalent LiO5 trigonal bipyramids, and a faceface with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 43–54°. There are a spread of Li–O bond distances ranging from 2.01–2.32 Å. In the tenth Li1+ site, Li1+ is bonded to five O2- atoms to form distorted LiO5 trigonal bipyramids that share corners with four MnO6 octahedra, corners with four MnO5 square pyramids, an edgeedge with one MnO5 square pyramid, and a faceface with one MnO6 octahedra. The corner-sharing octahedra tilt angles range from 37–58°. There are a spread of Li–O bond distances ranging from 2.02–2.21 Å. In the eleventh Li1+ site, Li1+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 1.91–2.40 Å. In the twelfth Li1+ site, Li1+ is bonded in a 1-coordinate geometry to five O2- atoms. There are a spread of Li–O bond distances ranging from 1.89–2.69 Å. There are sixteen inequivalent Mn+3.25+ sites. In the first Mn+3.25+ site, Mn+3.25+ is bonded to five O2- atoms to form MnO5 square pyramids that share corners with four MnO6 octahedra, corners with three LiO5 trigonal bipyramids, edges with two equivalent MnO5 square pyramids, and an edgeedge with one LiO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 46–54°. There are a spread of Mn–O bond distances ranging from 1.92–2.13 Å. In the second Mn+3.25+ site, Mn+3.25+ is bonded to five O2- atoms to form MnO5 square pyramids that share corners with four MnO6 octahedra, corners with three LiO5 trigonal bipyramids, edges with two equivalent MnO5 square pyramids, and an edgeedge with one LiO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 45–54°. There are a spread of Mn–O bond distances ranging from 1.91–2.11 Å. In the third Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO5 square pyramids, corners with three LiO5 trigonal bipyramids, edges with four MnO6 octahedra, and a faceface with one LiO5 trigonal bipyramid. There are a spread of Mn–O bond distances ranging from 1.89–2.08 Å. In the fourth Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO5 square pyramids, corners with three LiO5 trigonal bipyramids, edges with four MnO6 octahedra, and a faceface with one LiO5 trigonal bipyramid. There are a spread of Mn–O bond distances ranging from 1.90–2.24 Å. In the fifth Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO5 square pyramids, corners with three LiO5 trigonal bipyramids, edges with four MnO6 octahedra, and a faceface with one LiO5 trigonal bipyramid. There are a spread of Mn–O bond distances ranging from 1.89–2.07 Å. In the sixth Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO5 square pyramids, corners with three LiO5 trigonal bipyramids, edges with four MnO6 octahedra, and a faceface with one LiO5 trigonal bipyramid. There are a spread of Mn–O bond distances ranging from 1.90–2.25 Å. In the seventh Mn+3.25+ site, Mn+3.25+ is bonded to five O2- atoms to form MnO5 square pyramids that share corners with four MnO6 octahedra, corners with three LiO5 trigonal bipyramids, edges with two equivalent MnO5 square pyramids, and an edgeedge with one LiO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 47–54°. There are a spread of Mn–O bond distances ranging from 1.92–2.13 Å. In the eighth Mn+3.25+ site, Mn+3.25+ is bonded to five O2- atoms to form MnO5 square pyramids that share corners with four MnO6 octahedra, corners with three LiO5 trigonal bipyramids, edges with two equivalent MnO5 square pyramids, and an edgeedge with one LiO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 45–54°. There are a spread of Mn–O bond distances ranging from 1.91–2.11 Å. In the ninth Mn+3.25+ site, Mn+3.25+ is bonded to five O2- atoms to form MnO5 square pyramids that share corners with four MnO6 octahedra, corners with four LiO5 trigonal bipyramids, and edges with two equivalent MnO5 square pyramids. The corner-sharing octahedra tilt angles range from 49–51°. There are a spread of Mn–O bond distances ranging from 1.93–2.05 Å. In the tenth Mn+3.25+ site, Mn+3.25+ is bonded to five O2- atoms to form MnO5 square pyramids that share corners with four MnO6 octahedra, corners with two LiO5 trigonal bipyramids, edges with two equivalent MnO5 square pyramids, and an edgeedge with one LiO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 47–51°. There are a spread of Mn–O bond distances ranging from 1.90–2.14 Å. In the eleventh Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO5 square pyramids, corners with two LiO5 trigonal bipyramids, edges with four MnO6 octahedra, and a faceface with one LiO5 trigonal bipyramid. There are a spread of Mn–O bond distances ranging from 1.91–2.05 Å. In the twelfth Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO5 square pyramids, corners with four LiO5 trigonal bipyramids, and edges with four MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.94–2.17 Å. In the thirteenth Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO5 square pyramids, corners with four LiO5 trigonal bipyramids, and edges with four MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–2.17 Å. In the fourteenth Mn+3.25+ site, Mn+3.25+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with four MnO5 square pyramids, corners with two LiO5 trigonal bipyramids, edges with four MnO6 octahedra, and a faceface with one LiO5 trigonal bipyramid. There are a spread of Mn–O bond distances ranging from 1.91–2.06 Å. In the fifteenth Mn+3.25+ site, Mn+3.25+ is bonded to five O2- atoms to form MnO5 square pyramids that share corners with four MnO6 octahedra, corners with two LiO5 trigonal bipyramids, edges with two equivalent MnO5 square pyramids, and an edgeedge with one LiO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 46–52°. There are a spread of Mn–O bond distances ranging from 1.90–2.14 Å. In the sixteenth Mn+3.25+ site, Mn+3.25+ is bonded to five O2- atoms to form MnO5 square pyramids that share corners with four MnO6 octahedra, corners with four LiO5 trigonal bipyramids, and edges with two equivalent MnO5 square pyramids. The corner-sharing octahedra tilt angles range from 49–51°. There are a spread of Mn–O bond distances ranging from 1.92–2.05 Å. There are thirty-two inequivalent O2- sites. In the first O2- site, O2- is bonded to one Li1+ and three Mn+3.25+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with two equivalent OLiMn3 tetrahedra, a cornercorner with one OLi2Mn3 trigonal bipyramid, and an edgeedge with one OLi3Mn2 trigonal bipyramid. In the second O2- site, O2- is bonded to one Li1+ and three Mn+3.25+ atoms to form distorted OLiMn3 tetrahedra that share corners with two equivalent OLi3Mn2 trigonal bipyramids and corners with two equivalent OLiMn3 trigonal pyramids. In the third O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.25+ atoms. In the fourth O2- site, O2- is bonded to one Li1+ and three Mn+3.25+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with four OLiMn3 tetrahedra and an edgeedge with one OLi2Mn3 trigonal bipyramid. In the fifth O2- site, O2- is bonded to one Li1+ and three Mn+3.25+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with four OLiMn3 tetrahedra and an edgeedge with one OLi2Mn3 trigonal bipyramid. In the sixth O2- site, O2- is bonded in a distorted trigonal planar geometry to three Mn+3.25+ atoms. In the seventh O2- site, O2- is bonded to one Li1+ and three Mn+3.25+ atoms to form distorted OLiMn3 tetrahedra that share corners with two equivalent OLi3Mn2 trigonal bipyramids and corners with two equivalent OLiMn3 trigonal pyramids. In the eighth O2- site, O2- is bonded to one Li1+ and three Mn+3.25+ atoms to form distorted OLiMn3 trigonal pyramids that share corners with two equivalent OLiMn3 tetrahedra, a cornercorner with one OLi2Mn3 trigonal bipyramid, and an edgeedge with one OLi3Mn2 trigonal bipyramid. In the ninth O2- site, O2- is bonded to one Li1+ and three Mn+3.25+ atoms to form distorted OLiMn3 tetrahedra that share corners with two equivalent OLiMn3 tetrahedra, a cornercorner with one OLi3Mn2 trigonal bipyramid, corners with two OLiMn3 trigonal pyramids, and an edgeedge with one OLi2Mn3 trigonal bipyramid. In the tenth O2- site, O2- is bonded to one Li1+ and three Mn+3.25+ atoms to form distorted OLiMn3 tetrahedra that share corners with two equivalent OLiMn3 tetrahedra, a cornercorner with one OLi3Mn2 trigonal bipyramid, corners with two OLiMn3 trigonal pyramids, and an edgeedge with one OLi2Mn3 trigonal bipyramid. In the eleventh O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Mn+3.25+ atoms. In the twelfth O2-