Li3Mn2OF5 crystallizes in the orthorhombic F222 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(1)O2F4 octahedra, corners with two equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Mn(2)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Mn(3)O2F4 octahedra, and edges with three equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(4)O2F4 octahedra,  an edgeedge with one Mn(3)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Mn(2)F6 octahedra, and edges with two equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. In the third Li site, Li(3) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Mn(2)F6 octahedra, corners with four equivalent Li(1)O2F4 octahedra, edges with two equivalent Mn(2)F6 octahedra, edges with two equivalent Mn(1)O2F4 octahedra, and edges with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the fourth Li site, Li(4) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Mn(3)O2F4 octahedra, corners with four equivalent Li(2)F6 octahedra, edges with two equivalent Mn(3)O2F4 octahedra, edges with four equivalent Li(1)O2F4 octahedra, and edges with four equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. There are three 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(2) atoms to form MnO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with two equivalent Mn(2)F6 octahedra, corners with two equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Li(3)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Mn(3)O2F4 octahedra, and edges with three equivalent Li(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. In the second Mn site, Mn(2) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Mn(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and edges with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the third Mn site, Mn(3) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form MnO2F4 octahedra that share corners with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with four equivalent Li(1)O2F4 octahedra, and edges with four equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedra are not tilted. O(1) is bonded to one Li(4), two equivalent Li(1), one Mn(3), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(1)Li3Mn3 octahedra, corners with four equivalent F(1)Li3Mn2 square pyramids, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent F(1)Li3Mn2 square pyramids, and edges with eight equivalent F(2)Li3Mn2 square pyramids. The corner-sharing octahedra are not tilted. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), and one Mn(2) atom to form FLi3Mn2 square pyramids that share corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent F(2)Li3Mn2 square pyramids, corners with three equivalent F(1)Li3Mn2 square pyramids,  an edgeedge with one O(1)Li3Mn3 octahedra, edges with two equivalent F(2)Li3Mn2 square pyramids, and edges with three equivalent F(1)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles are 7°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(4), one Mn(1), and one Mn(3) atom to form FLi3Mn2 square pyramids that share corners with two equivalent F(1)Li3Mn2 square pyramids, corners with five equivalent F(2)Li3Mn2 square pyramids, edges with four equivalent O(1)Li3Mn3 octahedra, edges with two equivalent F(1)Li3Mn2 square pyramids, and edges with two equivalent F(2)Li3Mn2 square pyramids. In the third F site, F(3) is bonded in a square co-planar geometry to one Li(3), two equivalent Li(2), and one Mn(2) atom.
Li3Mn2OF5 crystallizes in the orthorhombic F222 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(1)O2F4 octahedra, corners with two equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Mn(2)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Mn(3)O2F4 octahedra, and edges with three equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-11°. Both Li(1)-O(1) bond lengths are 2.08 Å. Both Li(1)-F(1) bond lengths are 2.41 Å. Both Li(1)-F(2) bond lengths are 2.10 Å. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(2)F6 octahedra, corners with two equivalent Li(4)O2F4 octahedra,  an edgeedge with one Mn(3)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Mn(2)F6 octahedra, and edges with two equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 3-6°. Both Li(2)-F(1) bond lengths are 1.96 Å. Both Li(2)-F(2) bond lengths are 2.37 Å. Both Li(2)-F(3) bond lengths are 2.01 Å. In the third Li site, Li(3) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Mn(2)F6 octahedra, corners with four equivalent Li(1)O2F4 octahedra, edges with two equivalent Mn(2)F6 octahedra, edges with two equivalent Mn(1)O2F4 octahedra, and edges with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. Both Li(3)-F(3) bond lengths are 2.20 Å. All Li(3)-F(1) bond lengths are 2.08 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Mn(3)O2F4 octahedra, corners with four equivalent Li(2)F6 octahedra, edges with two equivalent Mn(3)O2F4 octahedra, edges with four equivalent Li(1)O2F4 octahedra, and edges with four equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. Both Li(4)-O(1) bond lengths are 2.17 Å. All Li(4)-F(2) bond lengths are 2.18 Å. There are three 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(2) atoms to form MnO2F4 octahedra that share corners with two equivalent Li(1)O2F4 octahedra, corners with two equivalent Mn(2)F6 octahedra, corners with two equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Li(3)F6 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Mn(3)O2F4 octahedra, and edges with three equivalent Li(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 1-12°. Both Mn(1)-O(1) bond lengths are 2.14 Å. Both Mn(1)-F(1) bond lengths are 2.24 Å. Both Mn(1)-F(2) bond lengths are 2.21 Å. In the second Mn site, Mn(2) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Mn(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(1)O2F4 octahedra, and edges with four equivalent Li(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. Both Mn(2)-F(3) bond lengths are 2.10 Å. All Mn(2)-F(1) bond lengths are 2.18 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form MnO2F4 octahedra that share corners with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with four equivalent Li(1)O2F4 octahedra, and edges with four equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedra are not tilted. Both Mn(3)-O(1) bond lengths are 2.12 Å. All Mn(3)-F(2) bond lengths are 2.17 Å. O(1) is bonded to one Li(4), two equivalent Li(1), one Mn(3), and two equivalent Mn(1) atoms to form OLi3Mn3 octahedra that share corners with two equivalent O(1)Li3Mn3 octahedra, corners with four equivalent F(1)Li3Mn2 square pyramids, edges with two equivalent O(1)Li3Mn3 octahedra, edges with two equivalent F(1)Li3Mn2 square pyramids, and edges with eight equivalent F(2)Li3Mn2 square pyramids. The corner-sharing octahedra are not tilted. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Mn(1), and one Mn(2) atom to form FLi3Mn2 square pyramids that share corners with two equivalent O(1)Li3Mn3 octahedra, corners with two equivalent F(2)Li3Mn2 square pyramids, corners with three equivalent F(1)Li3Mn2 square pyramids,  an edgeedge with one O(1)Li3Mn3 octahedra, edges with two equivalent F(2)Li3Mn2 square pyramids, and edges with three equivalent F(1)Li3Mn2 square pyramids. The corner-sharing octahedral tilt angles are 7°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(4), one Mn(1), and one Mn(3) atom to form FLi3Mn2 square pyramids that share corners with two equivalent F(1)Li3Mn2 square pyramids, corners with five equivalent F(2)Li3Mn2 square pyramids, edges with four equivalent O(1)Li3Mn3 octahedra, edges with two equivalent F(1)Li3Mn2 square pyramids, and edges with two equivalent F(2)Li3Mn2 square pyramids. In the third F site, F(3) is bonded in a square co-planar geometry to one Li(3), two equivalent Li(2), and one Mn(2) atom.