Li5NiO3F2 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(2), three equivalent O(1), and one F(1) atom to form LiO4F trigonal bipyramids that share corners with two equivalent Li(2)O2F3 square pyramids, corners with three equivalent Li(1)O4F trigonal bipyramids, edges with three equivalent Ni(1)O4F2 octahedra, edges with three equivalent Li(2)O2F3 square pyramids, and edges with two equivalent Li(1)O4F trigonal bipyramids. In the second Li site, Li(2) is bonded to one O(1), one O(2), and three equivalent F(1) atoms to form distorted LiO2F3 square pyramids that share corners with two equivalent Ni(1)O4F2 octahedra, corners with three equivalent Li(2)O2F3 square pyramids, corners with two equivalent Li(1)O4F trigonal bipyramids, edges with two equivalent Ni(1)O4F2 octahedra, edges with two equivalent Li(2)O2F3 square pyramids, and edges with three equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 10-12°. In the third Li site, Li(3) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent F(1) atoms. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form NiO4F2 octahedra that share corners with two equivalent Ni(1)O4F2 octahedra, corners with four equivalent Li(2)O2F3 square pyramids, edges with four equivalent Li(2)O2F3 square pyramids, and edges with six equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedra are not tilted. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), three equivalent Li(1), and one Ni(1) atom to form OLi5Ni octahedra that share corners with four equivalent O(1)Li5Ni octahedra, edges with two equivalent O(1)Li5Ni octahedra, edges with three equivalent O(2)Li4Ni2 octahedra, and edges with five equivalent F(1)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 0-22°. In the second O site, O(2) 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 two equivalent O(2)Li4Ni2 octahedra, corners with four equivalent F(1)Li5Ni octahedra, edges with four equivalent F(1)Li5Ni octahedra, and edges with six equivalent O(1)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 0-21°. F(1) is bonded to one Li(1), one Li(3), three equivalent Li(2), and one Ni(1) atom to form FLi5Ni octahedra that share corners with two equivalent O(2)Li4Ni2 octahedra, corners with four equivalent F(1)Li5Ni octahedra, edges with two equivalent O(2)Li4Ni2 octahedra, edges with two equivalent F(1)Li5Ni octahedra, and edges with five equivalent O(1)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 0-21°.
Li5NiO3F2 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(2), three equivalent O(1), and one F(1) atom to form LiO4F trigonal bipyramids that share corners with two equivalent Li(2)O2F3 square pyramids, corners with three equivalent Li(1)O4F trigonal bipyramids, edges with three equivalent Ni(1)O4F2 octahedra, edges with three equivalent Li(2)O2F3 square pyramids, and edges with two equivalent Li(1)O4F trigonal bipyramids. The Li(1)-O(2) bond length is 1.99 Å. There are two shorter (2.00 Å) and one longer (2.05 Å) Li(1)-O(1) bond length. The Li(1)-F(1) bond length is 2.18 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), and three equivalent F(1) atoms to form distorted LiO2F3 square pyramids that share corners with two equivalent Ni(1)O4F2 octahedra, corners with three equivalent Li(2)O2F3 square pyramids, corners with two equivalent Li(1)O4F trigonal bipyramids, edges with two equivalent Ni(1)O4F2 octahedra, edges with two equivalent Li(2)O2F3 square pyramids, and edges with three equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 10-12°. The Li(2)-O(1) bond length is 1.94 Å. The Li(2)-O(2) bond length is 2.09 Å. There are two shorter (1.99 Å) and one longer (2.03 Å) Li(2)-F(1) bond length. In the third Li site, Li(3) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent F(1) atoms. Both Li(3)-O(1) bond lengths are 1.92 Å. Both Li(3)-F(1) bond lengths are 2.13 Å. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form NiO4F2 octahedra that share corners with two equivalent Ni(1)O4F2 octahedra, corners with four equivalent Li(2)O2F3 square pyramids, edges with four equivalent Li(2)O2F3 square pyramids, and edges with six equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedra are not tilted. Both Ni(1)-O(1) bond lengths are 1.90 Å. Both Ni(1)-O(2) bond lengths are 1.96 Å. Both Ni(1)-F(1) bond lengths are 2.16 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), three equivalent Li(1), and one Ni(1) atom to form OLi5Ni octahedra that share corners with four equivalent O(1)Li5Ni octahedra, edges with two equivalent O(1)Li5Ni octahedra, edges with three equivalent O(2)Li4Ni2 octahedra, and edges with five equivalent F(1)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 0-22°. In the second O site, O(2) 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 two equivalent O(2)Li4Ni2 octahedra, corners with four equivalent F(1)Li5Ni octahedra, edges with four equivalent F(1)Li5Ni octahedra, and edges with six equivalent O(1)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 0-21°. F(1) is bonded to one Li(1), one Li(3), three equivalent Li(2), and one Ni(1) atom to form FLi5Ni octahedra that share corners with two equivalent O(2)Li4Ni2 octahedra, corners with four equivalent F(1)Li5Ni octahedra, edges with two equivalent O(2)Li4Ni2 octahedra, edges with two equivalent F(1)Li5Ni octahedra, and edges with five equivalent O(1)Li5Ni octahedra. The corner-sharing octahedral tilt angles range from 0-21°.