Materials Data on Li2Mn3O4F3 by Materials Project

Abstract

Li2Mn3O4F3 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 two O2- and two F1- atoms to form LiO2F2 tetrahedra that share a cornercorner with one LiO3F3 octahedra, corners with nine MnO3F3 octahedra, and a cornercorner with one LiO4F trigonal bipyramid. The corner-sharing octahedra tilt angles range from 46–73°. There are one shorter (2.07 Å) and one longer (2.18 Å) Li–O bond lengths. There are one shorter (1.98 Å) and one longer (2.03 Å) Li–F bond lengths. In the second Li1+ site, Li1+ is bonded to four O2- and one F1- atom to form distorted LiO4F trigonal bipyramids that share a cornercorner with one LiO3F3 octahedra, corners with five MnO3F3 octahedra, corners with two LiO2F2 tetrahedra, and edges with four MnO4F2 octahedra. The corner-sharing octahedra tilt angles range from 13–89°. There are a spread of Li–O bond distances ranging from 2.02–2.22 Å. The Li–F bond length is 2.29 Å. In the third Li1+ site, Li1+ is bonded to three O2- and three F1- atoms to form distorted LiO3F3 octahedra that share corners with four MnO4F2 octahedra, corners with two LiO2F2 tetrahedra, a cornercorner with one LiO4F trigonal bipyramid, and edges with six MnO3F3 octahedra. The corner-sharing octahedra tilt angles range from 3–30°. There are a spread of Li–O bond distances ranging from 2.08–2.63 Å. There are a spread of Li–F bond distances ranging from 2.00–2.20 Å. In the fourth Li1+ site, Li1+ is bonded to one O2- and three F1- atoms to form LiOF3 tetrahedra that share a cornercorner with one LiO3F3 octahedra, corners with nine MnO3F3 octahedra, and a cornercorner with one LiO4F trigonal bipyramid. The corner-sharing octahedra tilt angles range from 35–70°. The Li–O bond length is 1.99 Å. There are a spread of Li–F bond distances ranging from 1.96–2.01 Å. There are six inequivalent Mn3+ sites. In the first Mn3+ site, Mn3+ is bonded to three O2- and three F1- atoms to form MnO3F3 octahedra that share corners with four LiO2F2 tetrahedra, a cornercorner with one LiO4F trigonal bipyramid, an edgeedge with one LiO3F3 octahedra, and edges with five MnO4F2 octahedra. There is two shorter (1.94 Å) and one longer (1.97 Å) Mn–O bond length. There are a spread of Mn–F bond distances ranging from 1.98–2.24 Å. In the second Mn3+ site, Mn3+ is bonded to four O2- and two F1- atoms to form MnO4F2 octahedra that share corners with three LiO2F2 tetrahedra, a cornercorner with one LiO4F trigonal bipyramid, an edgeedge with one LiO3F3 octahedra, edges with five MnO3F3 octahedra, and an edgeedge with one LiO4F trigonal bipyramid. There are a spread of Mn–O bond distances ranging from 1.92–2.15 Å. There are one shorter (2.08 Å) and one longer (2.18 Å) Mn–F bond lengths. In the third Mn3+ site, Mn3+ is bonded to three O2- and three F1- atoms to form MnO3F3 octahedra that share corners with two LiO2F2 tetrahedra, a cornercorner with one LiO4F trigonal bipyramid, edges with two equivalent LiO3F3 octahedra, edges with five MnO3F3 octahedra, and an edgeedge with one LiO4F trigonal bipyramid. There are a spread of Mn–O bond distances ranging from 1.90–1.94 Å. There are a spread of Mn–F bond distances ranging from 1.98–2.28 Å. In the fourth Mn3+ site, Mn3+ is bonded to four O2- and two F1- atoms to form MnO4F2 octahedra that share a cornercorner with one LiO3F3 octahedra, corners with two LiO2F2 tetrahedra, a cornercorner with one LiO4F trigonal bipyramid, an edgeedge with one LiO3F3 octahedra, edges with five MnO3F3 octahedra, and an edgeedge with one LiO4F trigonal bipyramid. The corner-sharing octahedral tilt angles are 30°. There are a spread of Mn–O bond distances ranging from 1.88–2.06 Å. There are one shorter (2.16 Å) and one longer (2.26 Å) Mn–F bond lengths. In the fifth Mn3+ site, Mn3+ is bonded to four O2- and two F1- atoms to form MnO4F2 octahedra that share a cornercorner with one LiO3F3 octahedra, corners with three LiO2F2 tetrahedra, a cornercorner with one LiO4F trigonal bipyramid, an edgeedge with one LiO3F3 octahedra, and edges with five MnO3F3 octahedra. The corner-sharing octahedral tilt angles are 24°. There are a spread of Mn–O bond distances ranging from 1.86–2.05 Å. There are one shorter (2.13 Å) and one longer (2.29 Å) Mn–F bond lengths. In the sixth Mn3+ site, Mn3+ is bonded to four O2- and two F1- atoms to form MnO4F2 octahedra that share corners with two equivalent LiO3F3 octahedra, corners with four LiO2F2 tetrahedra, edges with five MnO3F3 octahedra, and an edgeedge with one LiO4F trigonal bipyramid. The corner-sharing octahedra tilt angles range from 3–15°. There are a spread of Mn–O bond distances ranging from 1.89–2.05 Å. There are one shorter (2.28 Å) and one longer (2.34 Å) Mn–F bond lengths. There are eight inequivalent O2- sites. In the first O2- site, O2- is bonded to one Li1+ and three Mn3+ atoms to form OLiMn3 tetrahedra that share corners with four OLiMn3 trigonal pyramids and an edgeedge with one OLi2Mn3 square pyramid. In the second O2- site, O2- is bonded in a distorted see-saw-like geometry to one Li1+ and three Mn3+ atoms. In the third O2- site, O2- is bonded to one Li1+ and three Mn3+ atoms to form distorted OLiMn3 trigonal pyramids that share a cornercorner with one OLiMn3 tetrahedra, corners with two OLiMn3 trigonal pyramids, an edgeedge with one OLi2Mn3 square pyramid, and an edgeedge with one OLiMn3 trigonal pyramid. In the fourth O2- site, O2- is bonded to one Li1+ and three Mn3+ atoms to form distorted OLiMn3 trigonal pyramids that share a cornercorner with one OLi2Mn3 square pyramid, a cornercorner with one OLiMn3 tetrahedra, corners with two OLiMn3 trigonal pyramids, and an edgeedge with one OLiMn3 trigonal pyramid. In the fifth O2- site, O2- is bonded to two Li1+ and two Mn3+ atoms to form distorted OLi2Mn2 trigonal pyramids that share corners with two equivalent OLiMn3 tetrahedra, corners with two OLiMn3 trigonal pyramids, and an edgeedge with one OLi2Mn3 square pyramid. In the sixth O2- site, O2- is bonded to two Li1+ and three Mn3+ atoms to form a mixture of distorted corner and edge-sharing OLi2Mn3 square pyramids. In the seventh O2- site, O2- is bonded in a distorted rectangular see-saw-like geometry to one Li1+ and three Mn3+ atoms. In the eighth O2- site, O2- is bonded in a trigonal planar geometry to one Li1+ and two Mn3+ atoms. There are six inequivalent F1- sites. In the first F1- site, F1- is bonded in a distorted trigonal planar geometry to one Li1+ and two Mn3+ atoms. In the second F1- site, F1- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two Mn3+ atoms. In the third F1- site, F1- is bonded in a rectangular see-saw-like geometry to two Li1+ and two Mn3+ atoms. In the fourth F1- site, F1- is bonded in a distorted rectangular see-saw-like geometry to two Li1+ and two Mn3+ atoms. In the fifth F1- site, F1- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Mn3+ atoms. In the sixth F1- site, F1- is bonded in a rectangular see-saw-like geometry to one Li1+ and three Mn3+ atoms.