DOE OSTI2020
LiMn3O6 crystallizes in the triclinic P1 space group. The structure is three-dimensional. there are four inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with six MnO6 octahedra, an edgeedge with one LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 8–22°. There are a spread of Li–O bond distances ranging from 1.99–2.51 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with six MnO6 octahedra, an edgeedge with one LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 9–24°. There are a spread of Li–O bond distances ranging from 1.98–2.52 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with six MnO6 octahedra, an edgeedge with one LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 12–22°. There are a spread of Li–O bond distances ranging from 2.02–2.42 Å. In the fourth Li1+ site, Li1+ is bonded to six O2- atoms to form distorted LiO6 octahedra that share corners with six MnO6 octahedra, an edgeedge with one LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 9–20°. There are a spread of Li–O bond distances ranging from 2.09–2.54 Å. There are twelve inequivalent Mn+3.67+ sites. In the first Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two equivalent LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 16–20°. There are a spread of Mn–O bond distances ranging from 1.93–1.98 Å. In the second Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share a cornercorner with one LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedral tilt angles are 12°. There are a spread of Mn–O bond distances ranging from 1.92–1.97 Å. In the third Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two equivalent LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 15–16°. There are a spread of Mn–O bond distances ranging from 1.92–1.98 Å. In the fourth Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share edges with two LiO6 octahedra and edges with six MnO6 octahedra. There are a spread of Mn–O bond distances ranging from 1.93–1.95 Å. In the fifth Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share a cornercorner with one LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedral tilt angles are 9°. There are a spread of Mn–O bond distances ranging from 1.89–1.99 Å. In the sixth Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 8–14°. There are a spread of Mn–O bond distances ranging from 1.88–2.00 Å. In the seventh Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 9–11°. There are a spread of Mn–O bond distances ranging from 1.92–1.96 Å. In the eighth Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two equivalent LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 12–17°. There are a spread of Mn–O bond distances ranging from 1.92–1.98 Å. In the ninth Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with two equivalent LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 16–22°. There are a spread of Mn–O bond distances ranging from 1.91–2.20 Å. In the tenth Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 18–24°. There are a spread of Mn–O bond distances ranging from 1.93–2.19 Å. In the eleventh Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 14–16°. There are a spread of Mn–O bond distances ranging from 1.89–2.14 Å. In the twelfth Mn+3.67+ site, Mn+3.67+ is bonded to six O2- atoms to form MnO6 octahedra that share corners with three LiO6 octahedra, edges with two LiO6 octahedra, and edges with six MnO6 octahedra. The corner-sharing octahedra tilt angles range from 20–22°. There are a spread of Mn–O bond distances ranging from 1.93–2.21 Å. There are twenty-four inequivalent O2- sites. In the first O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Mn+3.67+ atoms. In the second O2- site, O2- is bonded to two Li1+ and three Mn+3.67+ atoms to form distorted OLi2Mn3 square pyramids that share a cornercorner with one OLiMn3 trigonal pyramid, an edgeedge with one OLi2Mn3 square pyramid, and edges with three OLiMn3 trigonal pyramids. In the third O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+ and three Mn+3.67+ atoms. In the fourth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to three Mn+3.67+ atoms. In the fifth O2- site, O2- is bonded to two Li1+ and three Mn+3.67+ atoms to form distorted OLi2Mn3 square pyramids that share a cornercorner with one OLi2Mn3 square pyramid, corners with four OLiMn3 trigonal pyramids, an edgeedge with one OLi2Mn3 square pyramid, and edges with two OLiMn3 trigonal pyramids. In the sixth O2- site, O2- is bonded in a distorted see-saw-like geometry to one Li1+ and three Mn+3.67+ atoms. In the seventh O2- site, O2- is bonded to two Li1+ and three Mn+3.67+ atoms to form OLi2Mn3 square pyramids that share a cornercorner with one OLiMn3 trigonal pyramid, an edgeedge with one OLi2Mn3 square pyramid, and edges with three OLiMn3 trigonal pyramids. In the eighth O2- site, O2- is bonded in a 3-coordinate geometry to three Mn+3.67+ atoms. In the ninth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to three Mn+3.67+ atoms. In the tenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+ and three Mn+3.67+ atoms. In the eleventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+ and three Mn+3.67+ atoms. In the twelfth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Mn+3.67+ atoms. In the thirteenth O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+ and three Mn+3.67+ atoms. In the fourteenth O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Mn+3.67+ atoms. In the fifteenth O2- site, O2- is bonded to one Li1+ and three Mn+3.67+ atoms to form OLiMn3 trigonal pyramids that share a cornercorner with one OLi2Mn3 square pyramid, a cornercorner with one OLiMn3 trigonal pyramid, edges with two OLi2Mn3 square pyramids, and edges with two OLiMn3 trigonal pyramids. In the sixteenth O2- site, O2- is bonded to two Li1+ and three Mn+3.67+ atoms to form distorted OLi2Mn3 square pyramids that share a cornercorner with one OLi2Mn3 square pyramid, corners with four OLiMn3 trigonal pyramids, an edgeedge with one OLi2Mn3 square pyramid, and edges with two OLiMn3 trigonal pyramids. In the seventeenth O2- site, O2- is bonded to one Li1+ and three Mn+3.67+ atoms to form distorted OLiMn3 trigonal pyramids that share a cornercorner with one OLi2Mn3 square pyramid, edges with two OLi2Mn3 square pyramids, and edges with two OLiMn3 trigonal pyramids. In the eighteenth O2- site, O2- is bonded in a distorted trigonal non-coplanar geometry to three Mn+3.67+ atoms. In the nineteenth O2- site, O2- is bonded to one Li1+ and three Mn+3.67+ atoms to form OLiMn3 trigonal pyramids that share a cornercorner with one OLi2Mn3 square pyramid, edges with two OLi2Mn3 square pyramids, and edges with two OLiMn3 trigonal pyramids. In the twentieth O2- site, O2- is bonded to one Li1+ and three Mn+3.67+ atoms to form OLiMn3 trigonal pyramids that share corners with three equivalent OLi2Mn3 square pyramids, a cornercorner with one OLiMn3 trigonal pyramid, an edgeedge with one OLi2Mn3 square pyramid, and edges with two OLiMn3 trigonal pyramids. In the twenty-first O2- site, O2- is bonded to one Li1+ and three Mn+3.67+ atoms to form OLiMn3 trigonal pyramids that share corners with three equivalent OLi2Mn3 square pyramids, a cornercorner with one OLiMn3 trigonal pyramid, an edgeedge with one OLi2Mn3 square pyramid, and edges with two OLiMn3 trigonal pyramids. In the twenty-second O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Mn+3.67+ atoms. In the twenty-third O2- site, O2- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Mn+3.67+ atoms. In the twenty-fourth O2- site, O2- is bonded to one Li1+ and three Mn+3.67+ atoms to form distorted OLiMn3 trigonal pyramids that share a cornercorner with one OLi2Mn3 square pyramid, a cornercorner with one OLiMn3 trigonal pyramid, edges with two OLi2Mn3 square pyramids, and edges with two OLiMn3 trigonal pyramids.