LiMn5O3F5 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(2), one F(3), two equivalent F(1), and two equivalent F(2) atoms to form LiOF5 octahedra that share corners with three equivalent Mn(2)O2F2 tetrahedra, corners with three equivalent Mn(1)OF3 tetrahedra, edges with two equivalent Mn(4)O2F4 octahedra, and edges with four equivalent Mn(3)O3F3 octahedra. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one F(3), and two equivalent F(2) atoms to form MnOF3 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Mn(4)O2F4 octahedra, and corners with six equivalent Mn(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 53-65°. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form MnO2F2 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Mn(4)O2F4 octahedra, and corners with six equivalent Mn(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 50-65°. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(3) atom to form MnO3F3 octahedra that share corners with three equivalent Mn(2)O2F2 tetrahedra, corners with three equivalent Mn(1)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(3)O3F3 octahedra. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(3), two equivalent F(1), and two equivalent F(2) atoms to form MnO2F4 octahedra that share corners with three equivalent Mn(2)O2F2 tetrahedra, corners with three equivalent Mn(1)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with four equivalent Mn(3)O3F3 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Mn(2), one Mn(4), and two equivalent Mn(3) atoms to form corner-sharing OMn4 tetrahedra. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(2), and two equivalent Mn(3) atoms. In the third O site, O(3) is bonded to one Mn(1), one Mn(4), and two equivalent Mn(3) atoms to form corner-sharing OMn4 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(2), one Mn(3), and one Mn(4) atom. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), and two equivalent Mn(3) atoms.
LiMn5O3F5 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(2), one F(3), two equivalent F(1), and two equivalent F(2) atoms to form LiOF5 octahedra that share corners with three equivalent Mn(2)O2F2 tetrahedra, corners with three equivalent Mn(1)OF3 tetrahedra, edges with two equivalent Mn(4)O2F4 octahedra, and edges with four equivalent Mn(3)O3F3 octahedra. The Li(1)-O(2) bond length is 1.99 Å. The Li(1)-F(3) bond length is 2.38 Å. Both Li(1)-F(1) bond lengths are 2.20 Å. Both Li(1)-F(2) bond lengths are 2.13 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), one F(3), and two equivalent F(2) atoms to form MnOF3 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Mn(4)O2F4 octahedra, and corners with six equivalent Mn(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 53-65°. The Mn(1)-O(3) bond length is 2.01 Å. The Mn(1)-F(3) bond length is 2.10 Å. Both Mn(1)-F(2) bond lengths are 2.11 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form MnO2F2 tetrahedra that share corners with three equivalent Li(1)OF5 octahedra, corners with three equivalent Mn(4)O2F4 octahedra, and corners with six equivalent Mn(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 50-65°. The Mn(2)-O(1) bond length is 2.04 Å. The Mn(2)-O(2) bond length is 1.99 Å. Both Mn(2)-F(1) bond lengths are 2.17 Å. In the third Mn site, Mn(3) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(3) atom to form MnO3F3 octahedra that share corners with three equivalent Mn(2)O2F2 tetrahedra, corners with three equivalent Mn(1)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, edges with two equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(3)O3F3 octahedra. The Mn(3)-O(1) bond length is 2.13 Å. The Mn(3)-O(2) bond length is 2.09 Å. The Mn(3)-O(3) bond length is 2.11 Å. The Mn(3)-F(1) bond length is 2.34 Å. The Mn(3)-F(2) bond length is 2.32 Å. The Mn(3)-F(3) bond length is 2.35 Å. In the fourth Mn site, Mn(4) is bonded to one O(1), one O(3), two equivalent F(1), and two equivalent F(2) atoms to form MnO2F4 octahedra that share corners with three equivalent Mn(2)O2F2 tetrahedra, corners with three equivalent Mn(1)OF3 tetrahedra, edges with two equivalent Li(1)OF5 octahedra, and edges with four equivalent Mn(3)O3F3 octahedra. The Mn(4)-O(1) bond length is 2.06 Å. The Mn(4)-O(3) bond length is 2.08 Å. Both Mn(4)-F(1) bond lengths are 2.26 Å. Both Mn(4)-F(2) bond lengths are 2.30 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Mn(2), one Mn(4), and two equivalent Mn(3) atoms to form corner-sharing OMn4 tetrahedra. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(2), and two equivalent Mn(3) atoms. In the third O site, O(3) is bonded to one Mn(1), one Mn(4), and two equivalent Mn(3) atoms to form corner-sharing OMn4 tetrahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(2), one Mn(3), and one Mn(4) atom. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(1), one Mn(3), and one Mn(4) atom. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), and two equivalent Mn(3) atoms.