Li3MnOF4 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(4), and two equivalent F(3) atoms to form LiOF4 trigonal bipyramids that share corners with two equivalent Mn(1)O2F4 octahedra,  a cornercorner with one Li(2)OF4 trigonal bipyramid, corners with two equivalent Li(1)OF4 trigonal bipyramids,  a cornercorner with one Li(3)OF4 trigonal pyramid, edges with two equivalent Mn(1)O2F4 octahedra, edges with two equivalent Li(2)OF4 trigonal bipyramids, and edges with two equivalent Li(3)OF4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 11-53°. In the second Li site, Li(2) is bonded to one O(1), one F(2), one F(3), and two equivalent F(1) atoms to form distorted LiOF4 trigonal bipyramids that share corners with two equivalent Mn(1)O2F4 octahedra,  a cornercorner with one Li(1)OF4 trigonal bipyramid, corners with two equivalent Li(2)OF4 trigonal bipyramids,  a cornercorner with one Li(3)OF4 trigonal pyramid, edges with two equivalent Mn(1)O2F4 octahedra, edges with two equivalent Li(1)OF4 trigonal bipyramids, and  an edgeedge with one Li(3)OF4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 28-57°. In the third Li site, Li(3) is bonded to one O(1), one F(2), one F(3), and two equivalent F(4) atoms to form distorted LiOF4 trigonal pyramids that share corners with two equivalent Mn(1)O2F4 octahedra,  a cornercorner with one Li(1)OF4 trigonal bipyramid,  a cornercorner with one Li(2)OF4 trigonal bipyramid, corners with two equivalent Li(3)OF4 trigonal pyramids, edges with two equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Li(2)OF4 trigonal bipyramid, and edges with two equivalent Li(1)OF4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 28-66°. Mn(1) is bonded to two equivalent O(1), one F(1), one F(2), one F(3), and one F(4) atom to form distorted MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Li(1)OF4 trigonal bipyramids, corners with two equivalent Li(2)OF4 trigonal bipyramids, corners with two equivalent Li(3)OF4 trigonal pyramids, edges with two equivalent Li(1)OF4 trigonal bipyramids, edges with two equivalent Li(2)OF4 trigonal bipyramids, and edges with two equivalent Li(3)OF4 trigonal pyramids. The corner-sharing octahedral tilt angles are 24°. O(1) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Mn(1) atoms to form distorted OLi3Mn2 trigonal bipyramids that share corners with two equivalent O(1)Li3Mn2 trigonal bipyramids, corners with two equivalent F(3)Li4Mn trigonal bipyramids, and edges with two equivalent F(3)Li4Mn trigonal bipyramids. There are four inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one Mn(1) atom. In the third F site, F(3) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Mn(1) atom to form distorted FLi4Mn trigonal bipyramids that share corners with two equivalent O(1)Li3Mn2 trigonal bipyramids, corners with two equivalent F(3)Li4Mn trigonal bipyramids, and edges with two equivalent O(1)Li3Mn2 trigonal bipyramids. In the fourth F site, F(4) is bonded in a distorted square co-planar geometry to one Li(1), two equivalent Li(3), and one Mn(1) atom.
Li3MnOF4 crystallizes in the monoclinic Cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(4), and two equivalent F(3) atoms to form LiOF4 trigonal bipyramids that share corners with two equivalent Mn(1)O2F4 octahedra,  a cornercorner with one Li(2)OF4 trigonal bipyramid, corners with two equivalent Li(1)OF4 trigonal bipyramids,  a cornercorner with one Li(3)OF4 trigonal pyramid, edges with two equivalent Mn(1)O2F4 octahedra, edges with two equivalent Li(2)OF4 trigonal bipyramids, and edges with two equivalent Li(3)OF4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 11-53°. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-F(1) bond length is 2.09 Å. The Li(1)-F(4) bond length is 2.12 Å. Both Li(1)-F(3) bond lengths are 1.87 Å. In the second Li site, Li(2) is bonded to one O(1), one F(2), one F(3), and two equivalent F(1) atoms to form distorted LiOF4 trigonal bipyramids that share corners with two equivalent Mn(1)O2F4 octahedra,  a cornercorner with one Li(1)OF4 trigonal bipyramid, corners with two equivalent Li(2)OF4 trigonal bipyramids,  a cornercorner with one Li(3)OF4 trigonal pyramid, edges with two equivalent Mn(1)O2F4 octahedra, edges with two equivalent Li(1)OF4 trigonal bipyramids, and  an edgeedge with one Li(3)OF4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 28-57°. The Li(2)-O(1) bond length is 2.16 Å. The Li(2)-F(2) bond length is 1.87 Å. The Li(2)-F(3) bond length is 2.05 Å. Both Li(2)-F(1) bond lengths are 1.95 Å. In the third Li site, Li(3) is bonded to one O(1), one F(2), one F(3), and two equivalent F(4) atoms to form distorted LiOF4 trigonal pyramids that share corners with two equivalent Mn(1)O2F4 octahedra,  a cornercorner with one Li(1)OF4 trigonal bipyramid,  a cornercorner with one Li(2)OF4 trigonal bipyramid, corners with two equivalent Li(3)OF4 trigonal pyramids, edges with two equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Li(2)OF4 trigonal bipyramid, and edges with two equivalent Li(1)OF4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 28-66°. The Li(3)-O(1) bond length is 2.54 Å. The Li(3)-F(2) bond length is 1.89 Å. The Li(3)-F(3) bond length is 2.03 Å. Both Li(3)-F(4) bond lengths are 1.94 Å. Mn(1) is bonded to two equivalent O(1), one F(1), one F(2), one F(3), and one F(4) atom to form distorted MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with two equivalent Li(1)OF4 trigonal bipyramids, corners with two equivalent Li(2)OF4 trigonal bipyramids, corners with two equivalent Li(3)OF4 trigonal pyramids, edges with two equivalent Li(1)OF4 trigonal bipyramids, edges with two equivalent Li(2)OF4 trigonal bipyramids, and edges with two equivalent Li(3)OF4 trigonal pyramids. The corner-sharing octahedral tilt angles are 24°. Both Mn(1)-O(1) bond lengths are 1.91 Å. The Mn(1)-F(1) bond length is 2.02 Å. The Mn(1)-F(2) bond length is 2.03 Å. The Mn(1)-F(3) bond length is 2.44 Å. The Mn(1)-F(4) bond length is 2.00 Å. O(1) is bonded to one Li(1), one Li(2), one Li(3), and two equivalent Mn(1) atoms to form distorted OLi3Mn2 trigonal bipyramids that share corners with two equivalent O(1)Li3Mn2 trigonal bipyramids, corners with two equivalent F(3)Li4Mn trigonal bipyramids, and edges with two equivalent F(3)Li4Mn trigonal bipyramids. There are four inequivalent F sites. In the first F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Li(2), and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one Mn(1) atom. In the third F site, F(3) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Mn(1) atom to form distorted FLi4Mn trigonal bipyramids that share corners with two equivalent O(1)Li3Mn2 trigonal bipyramids, corners with two equivalent F(3)Li4Mn trigonal bipyramids, and edges with two equivalent O(1)Li3Mn2 trigonal bipyramids. In the fourth F site, F(4) is bonded in a distorted square co-planar geometry to one Li(1), two equivalent Li(3), and one Mn(1) atom.