Li4Ni2OF7 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(3), and two equivalent F(5) atoms to form LiOF3 tetrahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent Li(4)OF5 octahedra, and corners with six equivalent Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 53-61°. In the second Li site, Li(2) is bonded to one F(1), one F(2), and two equivalent F(4) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent Li(4)OF5 octahedra, and corners with six equivalent Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. In the third Li site, Li(3) is bonded to one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent Li(4)OF5 octahedra, and edges with four equivalent Ni(1)OF5 octahedra. In the fourth Li site, Li(4) is bonded to one O(1), one F(1), two equivalent F(4), and two equivalent F(5) atoms to form distorted LiOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, and edges with four equivalent Ni(1)OF5 octahedra. Ni(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form NiOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)OF5 octahedra, and edges with two equivalent Ni(1)OF5 octahedra. O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), and two equivalent Ni(1) atoms. 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(2), one Li(4), 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 Li(3), and two equivalent Ni(1) atoms. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), and two equivalent Ni(1) atoms. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Ni(1) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(3), one Li(4), and one Ni(1) atom to form a mixture of distorted edge and corner-sharing FLi3Ni trigonal pyramids.
Li4Ni2OF7 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one F(3), and two equivalent F(5) atoms to form LiOF3 tetrahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent Li(4)OF5 octahedra, and corners with six equivalent Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 53-61°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-F(3) bond length is 1.92 Å. Both Li(1)-F(5) bond lengths are 1.92 Å. In the second Li site, Li(2) is bonded to one F(1), one F(2), and two equivalent F(4) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(3)F6 octahedra, corners with three equivalent Li(4)OF5 octahedra, and corners with six equivalent Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. The Li(2)-F(1) bond length is 1.97 Å. The Li(2)-F(2) bond length is 1.95 Å. Both Li(2)-F(4) bond lengths are 1.94 Å. In the third Li site, Li(3) is bonded to one F(2), one F(3), two equivalent F(4), and two equivalent F(5) atoms to form LiF6 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent Li(4)OF5 octahedra, and edges with four equivalent Ni(1)OF5 octahedra. The Li(3)-F(2) bond length is 2.11 Å. The Li(3)-F(3) bond length is 2.07 Å. Both Li(3)-F(4) bond lengths are 2.04 Å. Both Li(3)-F(5) bond lengths are 2.06 Å. In the fourth Li site, Li(4) is bonded to one O(1), one F(1), two equivalent F(4), and two equivalent F(5) atoms to form distorted LiOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, and edges with four equivalent Ni(1)OF5 octahedra. The Li(4)-O(1) bond length is 2.46 Å. The Li(4)-F(1) bond length is 1.99 Å. Both Li(4)-F(4) bond lengths are 2.03 Å. Both Li(4)-F(5) bond lengths are 2.00 Å. Ni(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(5) atom to form NiOF5 octahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Li(1)OF3 tetrahedra, edges with two equivalent Li(3)F6 octahedra, edges with two equivalent Li(4)OF5 octahedra, and edges with two equivalent Ni(1)OF5 octahedra. The Ni(1)-O(1) bond length is 1.93 Å. The Ni(1)-F(1) bond length is 2.06 Å. The Ni(1)-F(2) bond length is 2.04 Å. The Ni(1)-F(3) bond length is 2.07 Å. The Ni(1)-F(4) bond length is 2.03 Å. The Ni(1)-F(5) bond length is 2.01 Å. O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(4), and two equivalent Ni(1) atoms. 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(2), one Li(4), 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 Li(3), and two equivalent Ni(1) atoms. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), and two equivalent Ni(1) atoms. In the fourth F site, F(4) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Ni(1) atom. In the fifth F site, F(5) is bonded to one Li(1), one Li(3), one Li(4), and one Ni(1) atom to form a mixture of distorted edge and corner-sharing FLi3Ni trigonal pyramids.