Li3Mn3(OF)4 is Hausmannite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form LiO2F2 tetrahedra that share corners with three equivalent Li(2)O2F4 octahedra, corners with three equivalent Mn(1)O2F4 octahedra, and corners with six equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 52-67°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form LiO2F4 octahedra that share corners with six equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Mn(1)O2F4 octahedra, and edges with four equivalent Mn(2)O4F2 octahedra. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2) and four equivalent F(1) atoms to form MnO2F4 octahedra that share corners with six equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with four equivalent Mn(2)O4F2 octahedra. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with six equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Mn(1)O2F4 octahedra, and edges with two equivalent Mn(2)O4F2 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), and two equivalent Mn(2) atoms to form distorted OLi2Mn2 trigonal pyramids that share corners with three equivalent O(2)LiMn3 tetrahedra, corners with three equivalent O(1)Li2Mn2 trigonal pyramids, and  an edgeedge with one O(2)LiMn3 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Mn(1), and two equivalent Mn(2) atoms to form OLiMn3 tetrahedra that share corners with three equivalent O(2)LiMn3 tetrahedra, corners with three equivalent O(1)Li2Mn2 trigonal pyramids, and  an edgeedge with one O(1)Li2Mn2 trigonal pyramid. F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one Mn(2) atom.
Li3Mn3(OF)4 is Hausmannite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form LiO2F2 tetrahedra that share corners with three equivalent Li(2)O2F4 octahedra, corners with three equivalent Mn(1)O2F4 octahedra, and corners with six equivalent Mn(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 52-67°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-O(2) bond length is 2.11 Å. Both Li(1)-F(1) bond lengths are 1.96 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form LiO2F4 octahedra that share corners with six equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Mn(1)O2F4 octahedra, and edges with four equivalent Mn(2)O4F2 octahedra. Both Li(2)-O(1) bond lengths are 2.13 Å. All Li(2)-F(1) bond lengths are 2.07 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(2) and four equivalent F(1) atoms to form MnO2F4 octahedra that share corners with six equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with four equivalent Mn(2)O4F2 octahedra. Both Mn(1)-O(2) bond lengths are 1.92 Å. All Mn(1)-F(1) bond lengths are 2.06 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with six equivalent Li(1)O2F2 tetrahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Mn(1)O2F4 octahedra, and edges with two equivalent Mn(2)O4F2 octahedra. Both Mn(2)-O(1) bond lengths are 1.91 Å. Both Mn(2)-O(2) bond lengths are 2.00 Å. Both Mn(2)-F(1) bond lengths are 2.31 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), and two equivalent Mn(2) atoms to form distorted OLi2Mn2 trigonal pyramids that share corners with three equivalent O(2)LiMn3 tetrahedra, corners with three equivalent O(1)Li2Mn2 trigonal pyramids, and  an edgeedge with one O(2)LiMn3 tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Mn(1), and two equivalent Mn(2) atoms to form OLiMn3 tetrahedra that share corners with three equivalent O(2)LiMn3 tetrahedra, corners with three equivalent O(1)Li2Mn2 trigonal pyramids, and  an edgeedge with one O(1)Li2Mn2 trigonal pyramid. F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one Mn(2) atom.