Li3Ni8(OF3)4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form LiO2F4 octahedra that share edges with two equivalent Ni(3)OF5 octahedra, edges with four equivalent Ni(2)O2F4 octahedra, and edges with four equivalent Ni(1)O4F2 octahedra. In the second Li site, Li(2) is bonded to one F(2), one F(3), and two equivalent F(4) atoms to form LiF4 tetrahedra that share corners with three equivalent Ni(3)OF5 octahedra and corners with six equivalent Ni(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. There are three inequivalent Ni sites. In the first Ni site, 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 six equivalent Ni(2)O2F4 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Ni(2)O2F4 octahedra, edges with two equivalent Ni(1)O4F2 octahedra, and edges with two equivalent Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form NiO2F4 octahedra that share corners with three equivalent Ni(1)O4F2 octahedra, corners with three equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)O2F4 octahedra,  an edgeedge with one Ni(1)O4F2 octahedra, edges with two equivalent Ni(2)O2F4 octahedra, and edges with two equivalent Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. In the third Ni site, Ni(3) is bonded to one O(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form NiOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)O2F4 octahedra, edges with two equivalent Ni(1)O4F2 octahedra, and edges with four equivalent Ni(2)O2F4 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Ni(1), and two equivalent Ni(2) atoms to form OLiNi4 square pyramids that share corners with three equivalent O(1)LiNi4 square pyramids, edges with three equivalent O(2)Ni5 square pyramids, and  an edgeedge with one F(3)LiNi3 trigonal pyramid. In the second O site, O(2) is bonded to one Ni(3), two equivalent Ni(1), and two equivalent Ni(2) atoms to form ONi5 square pyramids that share corners with two equivalent O(2)Ni5 square pyramids, corners with three equivalent F(3)LiNi3 trigonal pyramids, and edges with three equivalent O(1)LiNi4 square pyramids. There are four inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Ni(2) atoms. In the second F site, F(3) is bonded to one Li(2), one Ni(3), and two equivalent Ni(2) atoms to form distorted FLiNi3 trigonal pyramids that share corners with three equivalent O(2)Ni5 square pyramids and  an edgeedge with one O(1)LiNi4 square pyramid. In the third F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(2), and one Ni(3) atom. In the fourth F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom.
Li3Ni8(OF3)4 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form LiO2F4 octahedra that share edges with two equivalent Ni(3)OF5 octahedra, edges with four equivalent Ni(2)O2F4 octahedra, and edges with four equivalent Ni(1)O4F2 octahedra. Both Li(1)-O(1) bond lengths are 2.02 Å. All Li(1)-F(1) bond lengths are 2.02 Å. In the second Li site, Li(2) is bonded to one F(2), one F(3), and two equivalent F(4) atoms to form LiF4 tetrahedra that share corners with three equivalent Ni(3)OF5 octahedra and corners with six equivalent Ni(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. The Li(2)-F(2) bond length is 1.90 Å. The Li(2)-F(3) bond length is 1.96 Å. Both Li(2)-F(4) bond lengths are 1.86 Å. There are three inequivalent Ni sites. In the first Ni site, 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 six equivalent Ni(2)O2F4 octahedra, edges with two equivalent Li(1)O2F4 octahedra, edges with two equivalent Ni(2)O2F4 octahedra, edges with two equivalent Ni(1)O4F2 octahedra, and edges with two equivalent Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. Both Ni(1)-O(1) bond lengths are 2.03 Å. Both Ni(1)-O(2) bond lengths are 2.02 Å. Both Ni(1)-F(1) bond lengths are 2.24 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one F(1), one F(2), one F(3), and one F(4) atom to form NiO2F4 octahedra that share corners with three equivalent Ni(1)O4F2 octahedra, corners with three equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)O2F4 octahedra,  an edgeedge with one Ni(1)O4F2 octahedra, edges with two equivalent Ni(2)O2F4 octahedra, and edges with two equivalent Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 7-10°. The Ni(2)-O(1) bond length is 2.08 Å. The Ni(2)-O(2) bond length is 2.06 Å. The Ni(2)-F(1) bond length is 2.10 Å. The Ni(2)-F(2) bond length is 1.99 Å. The Ni(2)-F(3) bond length is 2.09 Å. The Ni(2)-F(4) bond length is 2.01 Å. In the third Ni site, Ni(3) is bonded to one O(2), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form NiOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)O2F4 octahedra, edges with two equivalent Ni(1)O4F2 octahedra, and edges with four equivalent Ni(2)O2F4 octahedra. The Ni(3)-O(2) bond length is 2.03 Å. The Ni(3)-F(3) bond length is 2.06 Å. Both Ni(3)-F(1) bond lengths are 2.05 Å. Both Ni(3)-F(4) bond lengths are 1.97 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Ni(1), and two equivalent Ni(2) atoms to form OLiNi4 square pyramids that share corners with three equivalent O(1)LiNi4 square pyramids, edges with three equivalent O(2)Ni5 square pyramids, and  an edgeedge with one F(3)LiNi3 trigonal pyramid. In the second O site, O(2) is bonded to one Ni(3), two equivalent Ni(1), and two equivalent Ni(2) atoms to form ONi5 square pyramids that share corners with two equivalent O(2)Ni5 square pyramids, corners with three equivalent F(3)LiNi3 trigonal pyramids, and edges with three equivalent O(1)LiNi4 square pyramids. There are four inequivalent F sites. In the first F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(2) and two equivalent Ni(2) atoms. In the second F site, F(3) is bonded to one Li(2), one Ni(3), and two equivalent Ni(2) atoms to form distorted FLiNi3 trigonal pyramids that share corners with three equivalent O(2)Ni5 square pyramids and  an edgeedge with one O(1)LiNi4 square pyramid. In the third F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Ni(2), and one Ni(3) atom. In the fourth F site, F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ni(1), one Ni(2), and one Ni(3) atom.