LiMn6O5F7 crystallizes in the monoclinic C2 space group. Li(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent F(4) atoms. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(4) atoms to form MnO2F4 octahedra that share corners with two equivalent Mn(3)O3F2 trigonal bipyramids, corners with four equivalent Mn(2)O3F2 trigonal bipyramids, and edges with two equivalent Mn(4)O2F4 octahedra. In the second Mn site, Mn(2) is bonded to one O(1), two equivalent O(2), one F(1), and one F(3) atom to form distorted MnO3F2 trigonal bipyramids that share corners with two equivalent Mn(1)O2F4 octahedra, corners with four equivalent Mn(4)O2F4 octahedra,  an edgeedge with one Mn(2)O3F2 trigonal bipyramid, and  an edgeedge with one Mn(3)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 43-59°. In the third Mn site, Mn(3) is bonded to one O(3), two equivalent O(1), and two equivalent F(3) atoms to form distorted MnO3F2 trigonal bipyramids that share corners with two equivalent Mn(1)O2F4 octahedra, corners with four equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(2)O3F2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-51°. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(3), one F(1), one F(2), one F(3), and one F(4) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(3)O3F2 trigonal bipyramids, corners with four equivalent Mn(2)O3F2 trigonal bipyramids,  an edgeedge with one Mn(1)O2F4 octahedra, and  an edgeedge with one Mn(4)O2F4 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Mn(4), and two equivalent Mn(2) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(3) and two equivalent Mn(4) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the second F site, F(2) is bonded in an L-shaped geometry to two equivalent Mn(4) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), and one Mn(4) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1), one Mn(1), and one Mn(4) atom.
LiMn6O5F7 crystallizes in the monoclinic C2 space group. Li(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent F(4) atoms. Both Li(1)-O(2) bond lengths are 2.04 Å. Both Li(1)-F(4) bond lengths are 1.82 Å. There are four inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(4) atoms to form MnO2F4 octahedra that share corners with two equivalent Mn(3)O3F2 trigonal bipyramids, corners with four equivalent Mn(2)O3F2 trigonal bipyramids, and edges with two equivalent Mn(4)O2F4 octahedra. Both Mn(1)-O(1) bond lengths are 1.93 Å. Both Mn(1)-F(1) bond lengths are 2.09 Å. Both Mn(1)-F(4) bond lengths are 2.10 Å. In the second Mn site, Mn(2) is bonded to one O(1), two equivalent O(2), one F(1), and one F(3) atom to form distorted MnO3F2 trigonal bipyramids that share corners with two equivalent Mn(1)O2F4 octahedra, corners with four equivalent Mn(4)O2F4 octahedra,  an edgeedge with one Mn(2)O3F2 trigonal bipyramid, and  an edgeedge with one Mn(3)O3F2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 43-59°. The Mn(2)-O(1) bond length is 2.00 Å. There is one shorter (2.02 Å) and one longer (2.08 Å) Mn(2)-O(2) bond length. The Mn(2)-F(1) bond length is 2.15 Å. The Mn(2)-F(3) bond length is 2.08 Å. In the third Mn site, Mn(3) is bonded to one O(3), two equivalent O(1), and two equivalent F(3) atoms to form distorted MnO3F2 trigonal bipyramids that share corners with two equivalent Mn(1)O2F4 octahedra, corners with four equivalent Mn(4)O2F4 octahedra, and edges with two equivalent Mn(2)O3F2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-51°. The Mn(3)-O(3) bond length is 2.02 Å. Both Mn(3)-O(1) bond lengths are 2.05 Å. Both Mn(3)-F(3) bond lengths are 2.17 Å. In the fourth Mn site, Mn(4) is bonded to one O(2), one O(3), one F(1), one F(2), one F(3), and one F(4) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(3)O3F2 trigonal bipyramids, corners with four equivalent Mn(2)O3F2 trigonal bipyramids,  an edgeedge with one Mn(1)O2F4 octahedra, and  an edgeedge with one Mn(4)O2F4 octahedra. The Mn(4)-O(2) bond length is 1.91 Å. The Mn(4)-O(3) bond length is 1.94 Å. The Mn(4)-F(1) bond length is 2.13 Å. The Mn(4)-F(2) bond length is 2.10 Å. The Mn(4)-F(3) bond length is 2.03 Å. The Mn(4)-F(4) bond length is 2.17 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(3) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Mn(4), and two equivalent Mn(2) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(3) and two equivalent Mn(4) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Mn(1), one Mn(2), and one Mn(4) atom. In the second F site, F(2) is bonded in an L-shaped geometry to two equivalent Mn(4) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), and one Mn(4) atom. In the fourth F site, F(4) is bonded in a T-shaped geometry to one Li(1), one Mn(1), and one Mn(4) atom.