Li5NiO3F is Corundum-derived structured and crystallizes in the monoclinic C2/m 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 a mixture of distorted edge and corner-sharing LiO3F trigonal pyramids. In the second Li site, Li(2) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form a mixture of edge and corner-sharing LiO3F trigonal pyramids. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to two equivalent O(2) and two equivalent F(1) atoms. Ni(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Ni(1) atoms to form OLi4Ni2 octahedra that share corners with four equivalent O(2)Li5Ni octahedra,  an edgeedge with one O(1)Li4Ni2 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with four equivalent O(2)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 3-31°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Ni(1) atom to form OLi5Ni octahedra that share corners with two equivalent O(1)Li4Ni2 octahedra, corners with two equivalent F(1)Li6 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with three equivalent O(2)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 3-36°. F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form FLi6 octahedra that share corners with four equivalent O(2)Li5Ni octahedra,  an edgeedge with one F(1)Li6 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, and edges with four equivalent O(2)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 5-36°.
Li5NiO3F is Corundum-derived structured and crystallizes in the monoclinic C2/m 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 a mixture of distorted edge and corner-sharing LiO3F trigonal pyramids. The Li(1)-O(1) bond length is 1.97 Å. There is one shorter (1.91 Å) and one longer (1.93 Å) Li(1)-O(2) bond length. The Li(1)-F(1) bond length is 2.01 Å. In the second Li site, Li(2) is bonded to one O(1), two equivalent O(2), and one F(1) atom to form a mixture of edge and corner-sharing LiO3F trigonal pyramids. The Li(2)-O(1) bond length is 1.96 Å. There is one shorter (1.93 Å) and one longer (2.01 Å) Li(2)-O(2) bond length. The Li(2)-F(1) bond length is 2.04 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to two equivalent O(2) and two equivalent F(1) atoms. Both Li(3)-O(2) bond lengths are 1.91 Å. Both Li(3)-F(1) bond lengths are 2.04 Å. Ni(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Ni(1)-O(1) bond lengths are 1.94 Å. Both Ni(1)-O(2) bond lengths are 1.91 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Ni(1) atoms to form OLi4Ni2 octahedra that share corners with four equivalent O(2)Li5Ni octahedra,  an edgeedge with one O(1)Li4Ni2 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with four equivalent O(2)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 3-31°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Ni(1) atom to form OLi5Ni octahedra that share corners with two equivalent O(1)Li4Ni2 octahedra, corners with two equivalent F(1)Li6 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, edges with two equivalent F(1)Li6 octahedra, and edges with three equivalent O(2)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 3-36°. F(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Li(3) atoms to form FLi6 octahedra that share corners with four equivalent O(2)Li5Ni octahedra,  an edgeedge with one F(1)Li6 octahedra, edges with two equivalent O(1)Li4Ni2 octahedra, and edges with four equivalent O(2)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 5-36°.