Li2Mn3F8 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(2), one F(3), and one F(4) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(1)F6 octahedra, corners with five equivalent Mn(2)F5 trigonal bipyramids, and  an edgeedge with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 67°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with two equivalent Li(1)F4 tetrahedra, corners with six equivalent Mn(2)F5 trigonal bipyramids, and edges with two equivalent Li(1)F4 tetrahedra. In the second Mn site, Mn(2) is bonded to one F(2), one F(3), one F(4), and two equivalent F(1) atoms to form MnF5 trigonal bipyramids that share corners with three equivalent Mn(1)F6 octahedra, corners with five equivalent Li(1)F4 tetrahedra, and corners with two equivalent Mn(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-57°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(2) atoms. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom.
Li2Mn3F8 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1), one F(2), one F(3), and one F(4) atom to form LiF4 tetrahedra that share  a cornercorner with one Mn(1)F6 octahedra, corners with five equivalent Mn(2)F5 trigonal bipyramids, and  an edgeedge with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 67°. The Li(1)-F(1) bond length is 1.91 Å. The Li(1)-F(2) bond length is 1.98 Å. The Li(1)-F(3) bond length is 1.92 Å. The Li(1)-F(4) bond length is 1.92 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form MnF6 octahedra that share corners with two equivalent Li(1)F4 tetrahedra, corners with six equivalent Mn(2)F5 trigonal bipyramids, and edges with two equivalent Li(1)F4 tetrahedra. Both Mn(1)-F(2) bond lengths are 2.29 Å. Both Mn(1)-F(3) bond lengths are 2.10 Å. Both Mn(1)-F(4) bond lengths are 2.11 Å. In the second Mn site, Mn(2) is bonded to one F(2), one F(3), one F(4), and two equivalent F(1) atoms to form MnF5 trigonal bipyramids that share corners with three equivalent Mn(1)F6 octahedra, corners with five equivalent Li(1)F4 tetrahedra, and corners with two equivalent Mn(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-57°. The Mn(2)-F(2) bond length is 2.11 Å. The Mn(2)-F(3) bond length is 2.09 Å. The Mn(2)-F(4) bond length is 2.09 Å. There is one shorter (2.10 Å) and one longer (2.11 Å) Mn(2)-F(1) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(2) atoms. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom.