Li2Mn3F8 crystallizes in the orthorhombic Cmce space group. Li(1) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form LiF4 tetrahedra that share corners with three equivalent Mn(2)F6 octahedra and corners with six equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 53-57°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form MnF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra, edges with two equivalent Mn(1)F6 octahedra, and edges with two equivalent Mn(2)F6 octahedra. In the second Mn site, Mn(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra and edges with four equivalent Mn(1)F6 octahedra. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(2), and two equivalent Mn(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms.
Li2Mn3F8 crystallizes in the orthorhombic Cmce space group. Li(1) is bonded to one F(2), one F(3), and two equivalent F(1) atoms to form LiF4 tetrahedra that share corners with three equivalent Mn(2)F6 octahedra and corners with six equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 53-57°. The Li(1)-F(2) bond length is 2.05 Å. The Li(1)-F(3) bond length is 1.91 Å. Both Li(1)-F(1) bond lengths are 1.94 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form MnF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra, edges with two equivalent Mn(1)F6 octahedra, and edges with two equivalent Mn(2)F6 octahedra. Both Mn(1)-F(1) bond lengths are 2.12 Å. Both Mn(1)-F(2) bond lengths are 2.28 Å. Both Mn(1)-F(3) bond lengths are 2.10 Å. In the second Mn site, Mn(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra and edges with four equivalent Mn(1)F6 octahedra. Both Mn(2)-F(2) bond lengths are 2.18 Å. All Mn(2)-F(1) bond lengths are 2.15 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(2), and two equivalent Mn(1) atoms. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms.