LiNi2OF3 crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(2), and two equivalent F(1) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Ni(3)OF5 octahedra, corners with two equivalent Ni(4)OF5 octahedra, corners with three equivalent Ni(1)OF5 octahedra, corners with four equivalent Ni(2)O3F3 octahedra, and  a cornercorner with one Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 52-66°. In the second Li site, Li(2) is bonded to one F(4), one F(5), and two equivalent F(3) atoms to form LiF4 tetrahedra that share  a cornercorner with one Ni(4)OF5 octahedra, corners with two equivalent Ni(3)OF5 octahedra, corners with three equivalent Ni(1)OF5 octahedra, corners with four equivalent Ni(2)O3F3 octahedra, and  a cornercorner with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-60°. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form NiOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra,  an edgeedge with one Ni(3)OF5 octahedra,  an edgeedge with one Ni(4)OF5 octahedra, and edges with four equivalent Ni(2)O3F3 octahedra. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one O(3), one F(1), one F(3), and one F(4) atom to form NiO3F3 octahedra that share corners with two equivalent Ni(2)O3F3 octahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(1)OF3 tetrahedra,  an edgeedge with one Ni(3)OF5 octahedra,  an edgeedge with one Ni(4)OF5 octahedra, edges with two equivalent Ni(1)OF5 octahedra, and edges with three equivalent Ni(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 14-17°. In the third Ni site, Ni(3) is bonded to one O(3), one F(2), and four equivalent F(3) atoms to form NiOF5 octahedra that share corners with two equivalent Li(1)OF3 tetrahedra, corners with four equivalent Li(2)F4 tetrahedra, edges with two equivalent Ni(1)OF5 octahedra, and edges with four equivalent Ni(2)O3F3 octahedra. In the fourth Ni site, Ni(4) is bonded to one O(2), one F(5), and four equivalent F(1) atoms to form NiOF5 octahedra that share corners with two equivalent Li(2)F4 tetrahedra, corners with four equivalent Li(1)OF3 tetrahedra, edges with two equivalent Ni(1)OF5 octahedra, and edges with four equivalent Ni(2)O3F3 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Ni(1), and two equivalent Ni(2) atoms to form distorted OLiNi3 tetrahedra that share corners with two equivalent O(3)Ni5 square pyramids, corners with three equivalent F(4)LiNi3 trigonal pyramids, and  an edgeedge with one O(2)Ni5 square pyramid. In the second O site, O(2) is bonded to one Ni(4) and four equivalent Ni(2) atoms to form ONi5 square pyramids that share corners with four equivalent F(4)LiNi3 trigonal pyramids, edges with two equivalent O(3)Ni5 square pyramids, and edges with two equivalent O(1)LiNi3 tetrahedra. In the third O site, O(3) is bonded to one Ni(3) and four equivalent Ni(2) atoms to form ONi5 square pyramids that share corners with four equivalent O(1)LiNi3 tetrahedra, edges with two equivalent O(2)Ni5 square pyramids, and edges with two equivalent F(4)LiNi3 trigonal pyramids. There are five inequivalent F sites. In the first 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(4) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Ni(3) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ni(1), one Ni(2), and one Ni(3) atom. In the fourth F site, F(4) is bonded to one Li(2), one Ni(1), and two equivalent Ni(2) atoms to form distorted FLiNi3 trigonal pyramids that share corners with two equivalent O(2)Ni5 square pyramids, corners with three equivalent O(1)LiNi3 tetrahedra, and  an edgeedge with one O(3)Ni5 square pyramid. In the fifth F site, F(5) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Ni(4) atom.
LiNi2OF3 crystallizes in the orthorhombic Imm2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(2), and two equivalent F(1) atoms to form LiOF3 tetrahedra that share  a cornercorner with one Ni(3)OF5 octahedra, corners with two equivalent Ni(4)OF5 octahedra, corners with three equivalent Ni(1)OF5 octahedra, corners with four equivalent Ni(2)O3F3 octahedra, and  a cornercorner with one Li(1)OF3 tetrahedra. The corner-sharing octahedral tilt angles range from 52-66°. The Li(1)-O(1) bond length is 1.93 Å. The Li(1)-F(2) bond length is 1.89 Å. Both Li(1)-F(1) bond lengths are 1.95 Å. In the second Li site, Li(2) is bonded to one F(4), one F(5), and two equivalent F(3) atoms to form LiF4 tetrahedra that share  a cornercorner with one Ni(4)OF5 octahedra, corners with two equivalent Ni(3)OF5 octahedra, corners with three equivalent Ni(1)OF5 octahedra, corners with four equivalent Ni(2)O3F3 octahedra, and  a cornercorner with one Li(2)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-60°. The Li(2)-F(4) bond length is 1.96 Å. The Li(2)-F(5) bond length is 1.85 Å. Both Li(2)-F(3) bond lengths are 1.92 Å. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one F(4), two equivalent F(1), and two equivalent F(3) atoms to form NiOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra,  an edgeedge with one Ni(3)OF5 octahedra,  an edgeedge with one Ni(4)OF5 octahedra, and edges with four equivalent Ni(2)O3F3 octahedra. The Ni(1)-O(1) bond length is 1.93 Å. The Ni(1)-F(4) bond length is 2.10 Å. Both Ni(1)-F(1) bond lengths are 2.07 Å. Both Ni(1)-F(3) bond lengths are 2.07 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one O(3), one F(1), one F(3), and one F(4) atom to form NiO3F3 octahedra that share corners with two equivalent Ni(2)O3F3 octahedra, corners with two equivalent Li(2)F4 tetrahedra, corners with two equivalent Li(1)OF3 tetrahedra,  an edgeedge with one Ni(3)OF5 octahedra,  an edgeedge with one Ni(4)OF5 octahedra, edges with two equivalent Ni(1)OF5 octahedra, and edges with three equivalent Ni(2)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 14-17°. The Ni(2)-O(1) bond length is 1.96 Å. The Ni(2)-O(2) bond length is 2.04 Å. The Ni(2)-O(3) bond length is 2.10 Å. The Ni(2)-F(1) bond length is 2.18 Å. The Ni(2)-F(3) bond length is 2.15 Å. The Ni(2)-F(4) bond length is 2.11 Å. In the third Ni site, Ni(3) is bonded to one O(3), one F(2), and four equivalent F(3) atoms to form NiOF5 octahedra that share corners with two equivalent Li(1)OF3 tetrahedra, corners with four equivalent Li(2)F4 tetrahedra, edges with two equivalent Ni(1)OF5 octahedra, and edges with four equivalent Ni(2)O3F3 octahedra. The Ni(3)-O(3) bond length is 2.01 Å. The Ni(3)-F(2) bond length is 1.95 Å. All Ni(3)-F(3) bond lengths are 2.08 Å. In the fourth Ni site, Ni(4) is bonded to one O(2), one F(5), and four equivalent F(1) atoms to form NiOF5 octahedra that share corners with two equivalent Li(2)F4 tetrahedra, corners with four equivalent Li(1)OF3 tetrahedra, edges with two equivalent Ni(1)OF5 octahedra, and edges with four equivalent Ni(2)O3F3 octahedra. The Ni(4)-O(2) bond length is 2.00 Å. The Ni(4)-F(5) bond length is 1.96 Å. All Ni(4)-F(1) bond lengths are 2.08 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Ni(1), and two equivalent Ni(2) atoms to form distorted OLiNi3 tetrahedra that share corners with two equivalent O(3)Ni5 square pyramids, corners with three equivalent F(4)LiNi3 trigonal pyramids, and  an edgeedge with one O(2)Ni5 square pyramid. In the second O site, O(2) is bonded to one Ni(4) and four equivalent Ni(2) atoms to form ONi5 square pyramids that share corners with four equivalent F(4)LiNi3 trigonal pyramids, edges with two equivalent O(3)Ni5 square pyramids, and edges with two equivalent O(1)LiNi3 tetrahedra. In the third O site, O(3) is bonded to one Ni(3) and four equivalent Ni(2) atoms to form ONi5 square pyramids that share corners with four equivalent O(1)LiNi3 tetrahedra, edges with two equivalent O(2)Ni5 square pyramids, and edges with two equivalent F(4)LiNi3 trigonal pyramids. There are five inequivalent F sites. In the first 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(4) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to two equivalent Li(1) and one Ni(3) atom. In the third F site, F(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ni(1), one Ni(2), and one Ni(3) atom. In the fourth F site, F(4) is bonded to one Li(2), one Ni(1), and two equivalent Ni(2) atoms to form distorted FLiNi3 trigonal pyramids that share corners with two equivalent O(2)Ni5 square pyramids, corners with three equivalent O(1)LiNi3 tetrahedra, and  an edgeedge with one O(3)Ni5 square pyramid. In the fifth F site, F(5) is bonded in a trigonal planar geometry to two equivalent Li(2) and one Ni(4) atom.