LiMn2F5 crystallizes in the orthorhombic Pnnm space group. Li(1) is bonded to one F(2), one F(3), and two equivalent F(4) atoms to form LiF4 tetrahedra that share corners with four equivalent Mn(1)F6 octahedra and corners with four equivalent Mn(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 54-66°. 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(4) atoms to form MnF6 octahedra that share corners with four equivalent Li(1)F4 tetrahedra, corners with four equivalent Mn(2)F5 trigonal bipyramids, and edges with two equivalent Mn(1)F6 octahedra. In the second Mn site, Mn(2) is bonded to one F(1), two equivalent F(3), and two equivalent F(4) atoms to form distorted MnF5 trigonal bipyramids that share corners with four equivalent Mn(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Mn(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 52-59°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Mn(2) atoms. 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.
LiMn2F5 crystallizes in the orthorhombic Pnnm space group. Li(1) is bonded to one F(2), one F(3), and two equivalent F(4) atoms to form LiF4 tetrahedra that share corners with four equivalent Mn(1)F6 octahedra and corners with four equivalent Mn(2)F5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 54-66°. The Li(1)-F(2) bond length is 1.90 Å. The Li(1)-F(3) bond length is 1.86 Å. Both Li(1)-F(4) bond lengths are 1.91 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(4) atoms to form MnF6 octahedra that share corners with four equivalent Li(1)F4 tetrahedra, corners with four equivalent Mn(2)F5 trigonal bipyramids, and edges with two equivalent Mn(1)F6 octahedra. Both Mn(1)-F(1) bond lengths are 2.17 Å. Both Mn(1)-F(2) bond lengths are 2.13 Å. Both Mn(1)-F(4) bond lengths are 2.17 Å. In the second Mn site, Mn(2) is bonded to one F(1), two equivalent F(3), and two equivalent F(4) atoms to form distorted MnF5 trigonal bipyramids that share corners with four equivalent Mn(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Mn(2)F5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 52-59°. The Mn(2)-F(1) bond length is 2.15 Å. There is one shorter (2.09 Å) and one longer (2.12 Å) Mn(2)-F(3) bond length. Both Mn(2)-F(4) bond lengths are 2.08 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Mn(2) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Mn(2) atoms. 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.