Li2Ni3OF6 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(5), and one F(6) atom to form LiF4 tetrahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Ni(3)OF5 octahedra, corners with three equivalent Ni(2)OF5 octahedra, and corners with four equivalent Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 52-63°. In the second Li site, Li(2) is bonded to two equivalent O(1), one F(2), one F(4), one F(5), and one F(6) atom to form LiO2F4 octahedra that share  a cornercorner with one Ni(2)OF5 octahedra,  a cornercorner with one Ni(3)OF5 octahedra, corners with two equivalent Ni(1)OF5 octahedra, corners with two equivalent Li(1)F4 tetrahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one Ni(1)OF5 octahedra, edges with two equivalent Ni(2)OF5 octahedra, and edges with three equivalent Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 5-17°. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one F(2), one F(3), one F(6), and two equivalent F(1) atoms to form NiOF5 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with four equivalent Li(1)F4 tetrahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one Ni(1)OF5 octahedra, edges with two equivalent Ni(2)OF5 octahedra, and edges with two equivalent Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. In the second Ni site, Ni(2) is bonded to one O(1), one F(1), one F(3), one F(5), and two equivalent F(4) atoms to form NiOF5 octahedra that share  a cornercorner with one Li(2)O2F4 octahedra, corners with three equivalent Li(1)F4 tetrahedra,  an edgeedge with one Ni(2)OF5 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Ni(1)OF5 octahedra, and edges with two equivalent Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles are 17°. In the third Ni site, Ni(3) is bonded to one O(1), one F(4), one F(5), one F(6), and two equivalent F(2) atoms to form NiOF5 octahedra that share  a cornercorner with one Li(2)O2F4 octahedra, corners with two equivalent Li(1)F4 tetrahedra,  an edgeedge with one Ni(3)OF5 octahedra, edges with two equivalent Ni(1)OF5 octahedra, edges with two equivalent Ni(2)OF5 octahedra, and edges with three equivalent Li(2)O2F4 octahedra. The corner-sharing octahedral tilt angles are 5°. O(1) is bonded to two equivalent Li(2), one Ni(1), one Ni(2), and one Ni(3) atom to form edge-sharing OLi2Ni3 square pyramids. There are six 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(2), and two equivalent Ni(1) atoms. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ni(1), and two equivalent Ni(3) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Ni(1), and one Ni(2) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ni(3), and two equivalent Ni(2) atoms. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Ni(2), and one Ni(3) atom. In the sixth F site, F(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Ni(1), and one Ni(3) atom.
Li2Ni3OF6 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(3), one F(5), and one F(6) atom to form LiF4 tetrahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with two equivalent Ni(3)OF5 octahedra, corners with three equivalent Ni(2)OF5 octahedra, and corners with four equivalent Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 52-63°. The Li(1)-F(1) bond length is 1.95 Å. The Li(1)-F(3) bond length is 1.90 Å. The Li(1)-F(5) bond length is 1.95 Å. The Li(1)-F(6) bond length is 1.98 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), one F(2), one F(4), one F(5), and one F(6) atom to form LiO2F4 octahedra that share  a cornercorner with one Ni(2)OF5 octahedra,  a cornercorner with one Ni(3)OF5 octahedra, corners with two equivalent Ni(1)OF5 octahedra, corners with two equivalent Li(1)F4 tetrahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one Ni(1)OF5 octahedra, edges with two equivalent Ni(2)OF5 octahedra, and edges with three equivalent Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 5-17°. There is one shorter (2.01 Å) and one longer (2.09 Å) Li(2)-O(1) bond length. The Li(2)-F(2) bond length is 2.20 Å. The Li(2)-F(4) bond length is 2.11 Å. The Li(2)-F(5) bond length is 2.11 Å. The Li(2)-F(6) bond length is 2.26 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one F(2), one F(3), one F(6), and two equivalent F(1) atoms to form NiOF5 octahedra that share corners with two equivalent Li(2)O2F4 octahedra, corners with four equivalent Li(1)F4 tetrahedra,  an edgeedge with one Li(2)O2F4 octahedra,  an edgeedge with one Ni(1)OF5 octahedra, edges with two equivalent Ni(2)OF5 octahedra, and edges with two equivalent Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 6-11°. The Ni(1)-O(1) bond length is 1.98 Å. The Ni(1)-F(2) bond length is 2.09 Å. The Ni(1)-F(3) bond length is 2.00 Å. The Ni(1)-F(6) bond length is 2.04 Å. There is one shorter (2.09 Å) and one longer (2.11 Å) Ni(1)-F(1) bond length. In the second Ni site, Ni(2) is bonded to one O(1), one F(1), one F(3), one F(5), and two equivalent F(4) atoms to form NiOF5 octahedra that share  a cornercorner with one Li(2)O2F4 octahedra, corners with three equivalent Li(1)F4 tetrahedra,  an edgeedge with one Ni(2)OF5 octahedra, edges with two equivalent Li(2)O2F4 octahedra, edges with two equivalent Ni(1)OF5 octahedra, and edges with two equivalent Ni(3)OF5 octahedra. The corner-sharing octahedral tilt angles are 17°. The Ni(2)-O(1) bond length is 1.97 Å. The Ni(2)-F(1) bond length is 2.07 Å. The Ni(2)-F(3) bond length is 2.02 Å. The Ni(2)-F(5) bond length is 2.05 Å. There is one shorter (2.04 Å) and one longer (2.13 Å) Ni(2)-F(4) bond length. In the third Ni site, Ni(3) is bonded to one O(1), one F(4), one F(5), one F(6), and two equivalent F(2) atoms to form NiOF5 octahedra that share  a cornercorner with one Li(2)O2F4 octahedra, corners with two equivalent Li(1)F4 tetrahedra,  an edgeedge with one Ni(3)OF5 octahedra, edges with two equivalent Ni(1)OF5 octahedra, edges with two equivalent Ni(2)OF5 octahedra, and edges with three equivalent Li(2)O2F4 octahedra. The corner-sharing octahedral tilt angles are 5°. The Ni(3)-O(1) bond length is 1.96 Å. The Ni(3)-F(4) bond length is 2.08 Å. The Ni(3)-F(5) bond length is 2.05 Å. The Ni(3)-F(6) bond length is 2.03 Å. Both Ni(3)-F(2) bond lengths are 2.08 Å. O(1) is bonded to two equivalent Li(2), one Ni(1), one Ni(2), and one Ni(3) atom to form edge-sharing OLi2Ni3 square pyramids. There are six 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(2), and two equivalent Ni(1) atoms. In the second F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ni(1), and two equivalent Ni(3) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Ni(1), and one Ni(2) atom. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ni(3), and two equivalent Ni(2) atoms. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Ni(2), and one Ni(3) atom. In the sixth F site, F(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Ni(1), and one Ni(3) atom.