Li3FeO2F is Aluminum carbonitride-derived structured and crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one Li(3)O3F tetrahedra, corners with two equivalent Li(1)O3F trigonal pyramids, corners with five equivalent Li(2)O2F2 trigonal pyramids, and edges with two equivalent Li(3)O3F tetrahedra. In the second Li site, Li(2) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form LiO2F2 trigonal pyramids that share  a cornercorner with one Li(3)O3F tetrahedra, corners with two equivalent Li(2)O2F2 trigonal pyramids, corners with five equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent Li(3)O3F tetrahedra. In the third Li site, Li(3) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent Li(3)O3F tetrahedra,  a cornercorner with one Li(2)O2F2 trigonal pyramid,  a cornercorner with one Li(1)O3F trigonal pyramid, edges with two equivalent Li(2)O2F2 trigonal pyramids, and edges with two equivalent Li(1)O3F trigonal pyramids. Fe(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), two equivalent O(1), and one F(1) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Fe(1) atoms to form distorted OLi4Fe2 octahedra that share corners with two equivalent O(1)Li4Fe2 octahedra,  a cornercorner with one O(2)Li4Fe trigonal bipyramid,  a cornercorner with one F(1)Li4Fe trigonal bipyramid,  an edgeedge with one O(1)Li4Fe2 octahedra, edges with three equivalent O(2)Li4Fe trigonal bipyramids, and edges with three equivalent F(1)Li4Fe trigonal bipyramids. The corner-sharing octahedral tilt angles are 47°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Fe(1) atom to form OLi4Fe trigonal bipyramids that share  a cornercorner with one O(1)Li4Fe2 octahedra, corners with two equivalent O(2)Li4Fe trigonal bipyramids, corners with four equivalent F(1)Li4Fe trigonal bipyramids, edges with three equivalent O(1)Li4Fe2 octahedra, and  an edgeedge with one F(1)Li4Fe trigonal bipyramid. The corner-sharing octahedral tilt angles are 13°. F(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and one Fe(1) atom to form distorted FLi4Fe trigonal bipyramids that share  a cornercorner with one O(1)Li4Fe2 octahedra, corners with two equivalent F(1)Li4Fe trigonal bipyramids, corners with four equivalent O(2)Li4Fe trigonal bipyramids, edges with three equivalent O(1)Li4Fe2 octahedra, and  an edgeedge with one O(2)Li4Fe trigonal bipyramid. The corner-sharing octahedral tilt angles are 3°.
Li3FeO2F is Aluminum carbonitride-derived structured and crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one Li(3)O3F tetrahedra, corners with two equivalent Li(1)O3F trigonal pyramids, corners with five equivalent Li(2)O2F2 trigonal pyramids, and edges with two equivalent Li(3)O3F tetrahedra. The Li(1)-O(1) bond length is 2.18 Å. Both Li(1)-O(2) bond lengths are 1.93 Å. The Li(1)-F(1) bond length is 1.92 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form LiO2F2 trigonal pyramids that share  a cornercorner with one Li(3)O3F tetrahedra, corners with two equivalent Li(2)O2F2 trigonal pyramids, corners with five equivalent Li(1)O3F trigonal pyramids, and edges with two equivalent Li(3)O3F tetrahedra. The Li(2)-O(1) bond length is 2.24 Å. The Li(2)-O(2) bond length is 1.93 Å. Both Li(2)-F(1) bond lengths are 1.95 Å. In the third Li site, Li(3) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form LiO3F tetrahedra that share corners with two equivalent Li(3)O3F tetrahedra,  a cornercorner with one Li(2)O2F2 trigonal pyramid,  a cornercorner with one Li(1)O3F trigonal pyramid, edges with two equivalent Li(2)O2F2 trigonal pyramids, and edges with two equivalent Li(1)O3F trigonal pyramids. The Li(3)-O(2) bond length is 1.97 Å. Both Li(3)-O(1) bond lengths are 1.96 Å. The Li(3)-F(1) bond length is 1.94 Å. Fe(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), two equivalent O(1), and one F(1) atom. The Fe(1)-O(2) bond length is 1.91 Å. There is one shorter (1.96 Å) and one longer (2.06 Å) Fe(1)-O(1) bond length. The Fe(1)-F(1) bond length is 2.45 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Fe(1) atoms to form distorted OLi4Fe2 octahedra that share corners with two equivalent O(1)Li4Fe2 octahedra,  a cornercorner with one O(2)Li4Fe trigonal bipyramid,  a cornercorner with one F(1)Li4Fe trigonal bipyramid,  an edgeedge with one O(1)Li4Fe2 octahedra, edges with three equivalent O(2)Li4Fe trigonal bipyramids, and edges with three equivalent F(1)Li4Fe trigonal bipyramids. The corner-sharing octahedral tilt angles are 47°. In the second O site, O(2) is bonded to one Li(2), one Li(3), two equivalent Li(1), and one Fe(1) atom to form OLi4Fe trigonal bipyramids that share  a cornercorner with one O(1)Li4Fe2 octahedra, corners with two equivalent O(2)Li4Fe trigonal bipyramids, corners with four equivalent F(1)Li4Fe trigonal bipyramids, edges with three equivalent O(1)Li4Fe2 octahedra, and  an edgeedge with one F(1)Li4Fe trigonal bipyramid. The corner-sharing octahedral tilt angles are 13°. F(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and one Fe(1) atom to form distorted FLi4Fe trigonal bipyramids that share  a cornercorner with one O(1)Li4Fe2 octahedra, corners with two equivalent F(1)Li4Fe trigonal bipyramids, corners with four equivalent O(2)Li4Fe trigonal bipyramids, edges with three equivalent O(1)Li4Fe2 octahedra, and  an edgeedge with one O(2)Li4Fe trigonal bipyramid. The corner-sharing octahedral tilt angles are 3°.