Li3Ni2OF5 crystallizes in the orthorhombic F222 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(4)O2F4 octahedra,  an edgeedge with one Ni(3)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Ni(2)F6 octahedra, and edges with two equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Ni(1)O2F4 octahedra,  an edgeedge with one Ni(2)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Ni(3)O2F4 octahedra, and edges with three equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. In the third Li site, Li(3) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Ni(2)F6 octahedra, corners with four equivalent Li(2)O2F4 octahedra, edges with two equivalent Ni(2)F6 octahedra, edges with two equivalent Ni(1)O2F4 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the fourth Li site, Li(4) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Ni(3)O2F4 octahedra, corners with four equivalent Li(1)F6 octahedra, edges with two equivalent Ni(3)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form NiO2F4 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Ni(2)F6 octahedra, corners with two equivalent Ni(1)O2F4 octahedra,  an edgeedge with one Li(3)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Ni(3)O2F4 octahedra, and edges with three equivalent Li(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the second Ni site, Ni(2) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form NiF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Ni(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third Ni site, Ni(3) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form NiO2F4 octahedra that share corners with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedra are not tilted. O(1) is bonded to one Li(4), two equivalent Li(2), one Ni(3), and two equivalent Ni(1) atoms to form OLi3Ni3 octahedra that share corners with two equivalent O(1)Li3Ni3 octahedra, corners with four equivalent F(1)Li3Ni2 square pyramids, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent F(1)Li3Ni2 square pyramids, and edges with eight equivalent F(2)Li3Ni2 square pyramids. The corner-sharing octahedra are not tilted. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Ni(1), and one Ni(2) atom to form FLi3Ni2 square pyramids that share corners with two equivalent O(1)Li3Ni3 octahedra, corners with two equivalent F(2)Li3Ni2 square pyramids, corners with three equivalent F(1)Li3Ni2 square pyramids,  an edgeedge with one O(1)Li3Ni3 octahedra, edges with two equivalent F(2)Li3Ni2 square pyramids, and edges with three equivalent F(1)Li3Ni2 square pyramids. The corner-sharing octahedral tilt angles range from 3-5°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(4), one Ni(1), and one Ni(3) atom to form FLi3Ni2 square pyramids that share corners with two equivalent F(1)Li3Ni2 square pyramids, corners with five equivalent F(2)Li3Ni2 square pyramids, edges with four equivalent O(1)Li3Ni3 octahedra, edges with two equivalent F(1)Li3Ni2 square pyramids, and edges with two equivalent F(2)Li3Ni2 square pyramids. In the third F site, F(3) is bonded in a square co-planar geometry to one Li(3), two equivalent Li(1), and one Ni(2) atom.
Li3Ni2OF5 crystallizes in the orthorhombic F222 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with two equivalent Li(4)O2F4 octahedra,  an edgeedge with one Ni(3)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Ni(2)F6 octahedra, and edges with two equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Li(1)-F(1) bond lengths are 1.96 Å. Both Li(1)-F(2) bond lengths are 2.20 Å. Both Li(1)-F(3) bond lengths are 1.96 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Ni(1)O2F4 octahedra,  an edgeedge with one Ni(2)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Ni(3)O2F4 octahedra, and edges with three equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. Both Li(2)-O(1) bond lengths are 2.04 Å. Both Li(2)-F(1) bond lengths are 2.17 Å. Both Li(2)-F(2) bond lengths are 2.12 Å. In the third Li site, Li(3) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form LiF6 octahedra that share corners with two equivalent Ni(2)F6 octahedra, corners with four equivalent Li(2)O2F4 octahedra, edges with two equivalent Ni(2)F6 octahedra, edges with two equivalent Ni(1)O2F4 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Li(3)-F(3) bond lengths are 2.20 Å. All Li(3)-F(1) bond lengths are 2.04 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form LiO2F4 octahedra that share corners with two equivalent Ni(3)O2F4 octahedra, corners with four equivalent Li(1)F6 octahedra, edges with two equivalent Ni(3)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Li(4)-O(1) bond lengths are 2.16 Å. All Li(4)-F(2) bond lengths are 2.09 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms to form NiO2F4 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Ni(2)F6 octahedra, corners with two equivalent Ni(1)O2F4 octahedra,  an edgeedge with one Li(3)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Ni(3)O2F4 octahedra, and edges with three equivalent Li(2)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Both Ni(1)-O(1) bond lengths are 2.02 Å. Both Ni(1)-F(1) bond lengths are 2.17 Å. Both Ni(1)-F(2) bond lengths are 2.06 Å. In the second Ni site, Ni(2) is bonded to two equivalent F(3) and four equivalent F(1) atoms to form NiF6 octahedra that share corners with two equivalent Li(3)F6 octahedra, corners with four equivalent Ni(1)O2F4 octahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(2)O2F4 octahedra, and edges with four equivalent Li(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. Both Ni(2)-F(3) bond lengths are 1.97 Å. All Ni(2)-F(1) bond lengths are 2.07 Å. In the third Ni site, Ni(3) is bonded to two equivalent O(1) and four equivalent F(2) atoms to form NiO2F4 octahedra that share corners with two equivalent Li(4)O2F4 octahedra, edges with two equivalent Li(1)F6 octahedra, edges with two equivalent Li(4)O2F4 octahedra, edges with four equivalent Li(2)O2F4 octahedra, and edges with four equivalent Ni(1)O2F4 octahedra. The corner-sharing octahedra are not tilted. Both Ni(3)-O(1) bond lengths are 2.02 Å. All Ni(3)-F(2) bond lengths are 2.06 Å. O(1) is bonded to one Li(4), two equivalent Li(2), one Ni(3), and two equivalent Ni(1) atoms to form OLi3Ni3 octahedra that share corners with two equivalent O(1)Li3Ni3 octahedra, corners with four equivalent F(1)Li3Ni2 square pyramids, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent F(1)Li3Ni2 square pyramids, and edges with eight equivalent F(2)Li3Ni2 square pyramids. The corner-sharing octahedra are not tilted. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(2), one Li(3), one Ni(1), and one Ni(2) atom to form FLi3Ni2 square pyramids that share corners with two equivalent O(1)Li3Ni3 octahedra, corners with two equivalent F(2)Li3Ni2 square pyramids, corners with three equivalent F(1)Li3Ni2 square pyramids,  an edgeedge with one O(1)Li3Ni3 octahedra, edges with two equivalent F(2)Li3Ni2 square pyramids, and edges with three equivalent F(1)Li3Ni2 square pyramids. The corner-sharing octahedral tilt angles range from 3-5°. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(4), one Ni(1), and one Ni(3) atom to form FLi3Ni2 square pyramids that share corners with two equivalent F(1)Li3Ni2 square pyramids, corners with five equivalent F(2)Li3Ni2 square pyramids, edges with four equivalent O(1)Li3Ni3 octahedra, edges with two equivalent F(1)Li3Ni2 square pyramids, and edges with two equivalent F(2)Li3Ni2 square pyramids. In the third F site, F(3) is bonded in a square co-planar geometry to one Li(3), two equivalent Li(1), and one Ni(2) atom.