Li4MnOF5 crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(3), one F(5), and two equivalent F(4) atoms to form distorted LiOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra,  a cornercorner with one Li(3)OF4 trigonal bipyramid, corners with two equivalent Li(4)OF4 trigonal bipyramids, edges with two equivalent Li(2)OF5 octahedra, edges with three equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Li(3)OF4 trigonal bipyramid, and  an edgeedge with one Li(4)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 0-32°. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(4), and two equivalent F(5) atoms to form distorted LiOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra,  a cornercorner with one Li(4)OF4 trigonal bipyramid, corners with two equivalent Li(3)OF4 trigonal bipyramids, edges with two equivalent Li(1)OF5 octahedra, edges with three equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Li(3)OF4 trigonal bipyramid, and  an edgeedge with one Li(4)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 0-31°. In the third Li site, Li(3) is bonded to one O(1), one F(1), one F(3), and two equivalent F(2) atoms to form distorted LiOF4 trigonal bipyramids that share  a cornercorner with one Li(1)OF5 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(3)OF4 trigonal bipyramids, corners with two equivalent Li(4)OF4 trigonal bipyramids,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Li(2)OF5 octahedra, edges with two equivalent Mn(1)O2F4 octahedra, and edges with two equivalent Li(4)OF4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 1-73°. In the fourth Li site, Li(4) is bonded to one O(1), one F(1), one F(2), and two equivalent F(3) atoms to form distorted LiOF4 trigonal bipyramids that share  a cornercorner with one Li(2)OF5 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra, corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(3)OF4 trigonal bipyramids, corners with two equivalent Li(4)OF4 trigonal bipyramids,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Li(2)OF5 octahedra, edges with two equivalent Mn(1)O2F4 octahedra, and edges with two equivalent Li(3)OF4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 1-73°. Mn(1) is bonded to two equivalent O(1), one F(2), one F(3), one F(4), and one F(5) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra,  a cornercorner with one Li(3)OF4 trigonal bipyramid,  a cornercorner with one Li(4)OF4 trigonal bipyramid, edges with three equivalent Li(1)OF5 octahedra, edges with three equivalent Li(2)OF5 octahedra, edges with two equivalent Li(3)OF4 trigonal bipyramids, and edges with two equivalent Li(4)OF4 trigonal bipyramids. The corner-sharing octahedra are not tilted. O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and two equivalent Mn(1) atoms to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent F(2)Li4Mn trigonal bipyramids, corners with two equivalent F(3)Li4Mn trigonal bipyramids,  a cornercorner with one F(4)Li3Mn trigonal pyramid,  a cornercorner with one F(5)Li3Mn trigonal pyramid, edges with two equivalent F(2)Li4Mn trigonal bipyramids, edges with two equivalent F(3)Li4Mn trigonal bipyramids, edges with two equivalent F(4)Li3Mn trigonal pyramids, and edges with two equivalent F(5)Li3Mn trigonal pyramids. The corner-sharing octahedra are not tilted. There are five inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to one Li(1), one Li(2), one Li(3), and one Li(4) atom. In the second F site, F(2) is bonded to one Li(2), one Li(4), two equivalent Li(3), and one Mn(1) atom to form FLi4Mn trigonal bipyramids that share corners with two equivalent O(1)Li4Mn2 octahedra,  a cornercorner with one F(3)Li4Mn trigonal bipyramid, corners with two equivalent F(2)Li4Mn trigonal bipyramids, corners with three equivalent F(5)Li3Mn trigonal pyramids, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent F(3)Li4Mn trigonal bipyramids, and  an edgeedge with one F(4)Li3Mn trigonal pyramid. The corner-sharing octahedral tilt angles range from 7-16°. In the third F site, F(3) is bonded to one Li(1), one Li(3), two equivalent Li(4), and one Mn(1) atom to form FLi4Mn trigonal bipyramids that share corners with two equivalent O(1)Li4Mn2 octahedra,  a cornercorner with one F(2)Li4Mn trigonal bipyramid, corners with two equivalent F(3)Li4Mn trigonal bipyramids, corners with three equivalent F(4)Li3Mn trigonal pyramids, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn trigonal bipyramids, and  an edgeedge with one F(5)Li3Mn trigonal pyramid. The corner-sharing octahedral tilt angles range from 8-16°. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share  a cornercorner with one O(1)Li4Mn2 octahedra, corners with three equivalent F(3)Li4Mn trigonal bipyramids,  a cornercorner with one F(5)Li3Mn trigonal pyramid, corners with two equivalent F(4)Li3Mn trigonal pyramids, edges with two equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one F(2)Li4Mn trigonal bipyramid, and edges with two equivalent F(5)Li3Mn trigonal pyramids. The corner-sharing octahedral tilt angles are 88°. In the fifth F site, F(5) is bonded to one Li(1), two equivalent Li(2), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share  a cornercorner with one O(1)Li4Mn2 octahedra, corners with three equivalent F(2)Li4Mn trigonal bipyramids,  a cornercorner with one F(4)Li3Mn trigonal pyramid, corners with two equivalent F(5)Li3Mn trigonal pyramids, edges with two equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one F(3)Li4Mn trigonal bipyramid, and edges with two equivalent F(4)Li3Mn trigonal pyramids. The corner-sharing octahedral tilt angles are 89°.
Li4MnOF5 crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(1), one F(3), one F(5), and two equivalent F(4) atoms to form distorted LiOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra,  a cornercorner with one Li(3)OF4 trigonal bipyramid, corners with two equivalent Li(4)OF4 trigonal bipyramids, edges with two equivalent Li(2)OF5 octahedra, edges with three equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Li(3)OF4 trigonal bipyramid, and  an edgeedge with one Li(4)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 0-32°. The Li(1)-O(1) bond length is 2.39 Å. The Li(1)-F(1) bond length is 1.97 Å. The Li(1)-F(3) bond length is 2.01 Å. The Li(1)-F(5) bond length is 2.24 Å. Both Li(1)-F(4) bond lengths are 1.96 Å. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(2), one F(4), and two equivalent F(5) atoms to form distorted LiOF5 octahedra that share corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(2)OF5 octahedra,  a cornercorner with one Li(4)OF4 trigonal bipyramid, corners with two equivalent Li(3)OF4 trigonal bipyramids, edges with two equivalent Li(1)OF5 octahedra, edges with three equivalent Mn(1)O2F4 octahedra,  an edgeedge with one Li(3)OF4 trigonal bipyramid, and  an edgeedge with one Li(4)OF4 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 0-31°. The Li(2)-O(1) bond length is 2.39 Å. The Li(2)-F(1) bond length is 1.98 Å. The Li(2)-F(2) bond length is 2.02 Å. The Li(2)-F(4) bond length is 2.23 Å. Both Li(2)-F(5) bond lengths are 1.95 Å. In the third Li site, Li(3) is bonded to one O(1), one F(1), one F(3), and two equivalent F(2) atoms to form distorted LiOF4 trigonal bipyramids that share  a cornercorner with one Li(1)OF5 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra, corners with two equivalent Li(2)OF5 octahedra, corners with two equivalent Li(3)OF4 trigonal bipyramids, corners with two equivalent Li(4)OF4 trigonal bipyramids,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Li(2)OF5 octahedra, edges with two equivalent Mn(1)O2F4 octahedra, and edges with two equivalent Li(4)OF4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 1-73°. The Li(3)-O(1) bond length is 2.30 Å. The Li(3)-F(1) bond length is 1.89 Å. The Li(3)-F(3) bond length is 2.00 Å. Both Li(3)-F(2) bond lengths are 2.00 Å. In the fourth Li site, Li(4) is bonded to one O(1), one F(1), one F(2), and two equivalent F(3) atoms to form distorted LiOF4 trigonal bipyramids that share  a cornercorner with one Li(2)OF5 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra, corners with two equivalent Li(1)OF5 octahedra, corners with two equivalent Li(3)OF4 trigonal bipyramids, corners with two equivalent Li(4)OF4 trigonal bipyramids,  an edgeedge with one Li(1)OF5 octahedra,  an edgeedge with one Li(2)OF5 octahedra, edges with two equivalent Mn(1)O2F4 octahedra, and edges with two equivalent Li(3)OF4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 1-73°. The Li(4)-O(1) bond length is 2.31 Å. The Li(4)-F(1) bond length is 1.89 Å. The Li(4)-F(2) bond length is 2.00 Å. Both Li(4)-F(3) bond lengths are 2.00 Å. Mn(1) is bonded to two equivalent O(1), one F(2), one F(3), one F(4), and one F(5) atom to form MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra,  a cornercorner with one Li(3)OF4 trigonal bipyramid,  a cornercorner with one Li(4)OF4 trigonal bipyramid, edges with three equivalent Li(1)OF5 octahedra, edges with three equivalent Li(2)OF5 octahedra, edges with two equivalent Li(3)OF4 trigonal bipyramids, and edges with two equivalent Li(4)OF4 trigonal bipyramids. The corner-sharing octahedra are not tilted. Both Mn(1)-O(1) bond lengths are 1.88 Å. The Mn(1)-F(2) bond length is 2.22 Å. The Mn(1)-F(3) bond length is 2.22 Å. The Mn(1)-F(4) bond length is 1.95 Å. The Mn(1)-F(5) bond length is 1.95 Å. O(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), and two equivalent Mn(1) atoms to form distorted OLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with two equivalent F(2)Li4Mn trigonal bipyramids, corners with two equivalent F(3)Li4Mn trigonal bipyramids,  a cornercorner with one F(4)Li3Mn trigonal pyramid,  a cornercorner with one F(5)Li3Mn trigonal pyramid, edges with two equivalent F(2)Li4Mn trigonal bipyramids, edges with two equivalent F(3)Li4Mn trigonal bipyramids, edges with two equivalent F(4)Li3Mn trigonal pyramids, and edges with two equivalent F(5)Li3Mn trigonal pyramids. The corner-sharing octahedra are not tilted. There are five inequivalent F sites. In the first F site, F(1) is bonded in a square co-planar geometry to one Li(1), one Li(2), one Li(3), and one Li(4) atom. In the second F site, F(2) is bonded to one Li(2), one Li(4), two equivalent Li(3), and one Mn(1) atom to form FLi4Mn trigonal bipyramids that share corners with two equivalent O(1)Li4Mn2 octahedra,  a cornercorner with one F(3)Li4Mn trigonal bipyramid, corners with two equivalent F(2)Li4Mn trigonal bipyramids, corners with three equivalent F(5)Li3Mn trigonal pyramids, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent F(3)Li4Mn trigonal bipyramids, and  an edgeedge with one F(4)Li3Mn trigonal pyramid. The corner-sharing octahedral tilt angles range from 7-16°. In the third F site, F(3) is bonded to one Li(1), one Li(3), two equivalent Li(4), and one Mn(1) atom to form FLi4Mn trigonal bipyramids that share corners with two equivalent O(1)Li4Mn2 octahedra,  a cornercorner with one F(2)Li4Mn trigonal bipyramid, corners with two equivalent F(3)Li4Mn trigonal bipyramids, corners with three equivalent F(4)Li3Mn trigonal pyramids, edges with two equivalent O(1)Li4Mn2 octahedra, edges with two equivalent F(2)Li4Mn trigonal bipyramids, and  an edgeedge with one F(5)Li3Mn trigonal pyramid. The corner-sharing octahedral tilt angles range from 8-16°. In the fourth F site, F(4) is bonded to one Li(2), two equivalent Li(1), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share  a cornercorner with one O(1)Li4Mn2 octahedra, corners with three equivalent F(3)Li4Mn trigonal bipyramids,  a cornercorner with one F(5)Li3Mn trigonal pyramid, corners with two equivalent F(4)Li3Mn trigonal pyramids, edges with two equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one F(2)Li4Mn trigonal bipyramid, and edges with two equivalent F(5)Li3Mn trigonal pyramids. The corner-sharing octahedral tilt angles are 88°. In the fifth F site, F(5) is bonded to one Li(1), two equivalent Li(2), and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share  a cornercorner with one O(1)Li4Mn2 octahedra, corners with three equivalent F(2)Li4Mn trigonal bipyramids,  a cornercorner with one F(4)Li3Mn trigonal pyramid, corners with two equivalent F(5)Li3Mn trigonal pyramids, edges with two equivalent O(1)Li4Mn2 octahedra,  an edgeedge with one F(3)Li4Mn trigonal bipyramid, and edges with two equivalent F(4)Li3Mn trigonal pyramids. The corner-sharing octahedral tilt angles are 89°.