Li4Co2OF7 is Spinel-derived structured and crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), one F(4), and one F(5) atom to form LiF4 tetrahedra that share corners with three equivalent Li(4)F6 octahedra, corners with three equivalent Li(3)OF5 octahedra, corners with three equivalent Co(1)OF5 octahedra, and corners with three equivalent Co(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(6), and one F(7) atom to form LiOF3 tetrahedra that share corners with three equivalent Li(4)F6 octahedra, corners with three equivalent Li(3)OF5 octahedra, corners with three equivalent Co(1)OF5 octahedra, and corners with three equivalent Co(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 53-61°. In the third Li site, Li(3) is bonded to one O(1), one F(3), one F(4), one F(5), one F(6), and one F(7) atom to form LiOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Co(1)OF5 octahedra, and edges with two equivalent Co(2)OF5 octahedra. In the fourth Li site, Li(4) is bonded to one F(1), one F(2), one F(4), one F(5), one F(6), and one F(7) atom to form LiF6 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with two equivalent Li(3)OF5 octahedra, edges with two equivalent Co(1)OF5 octahedra, and edges with two equivalent Co(2)OF5 octahedra. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(3)OF5 octahedra, and edges with two equivalent Co(2)OF5 octahedra. In the second Co site, Co(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(5), and one F(7) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(3)OF5 octahedra, and edges with two equivalent Co(1)OF5 octahedra. O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(1), and one Co(2) atom. There are seven 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), one Co(1), and one Co(2) atom. In the second F site, F(2) is bonded to one Li(1), one Li(4), one Co(1), and one Co(2) atom to form a mixture of distorted corner and edge-sharing FLi2Co2 trigonal pyramids. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Co(1), and one Co(2) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(3), one Li(4), and one Co(1) atom to form a mixture of distorted corner and edge-sharing FLi3Co trigonal pyramids. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one Co(2) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Co(1) atom. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Co(2) atom.
Li4Co2OF7 is Spinel-derived structured and crystallizes in the monoclinic Pc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(2), one F(3), one F(4), and one F(5) atom to form LiF4 tetrahedra that share corners with three equivalent Li(4)F6 octahedra, corners with three equivalent Li(3)OF5 octahedra, corners with three equivalent Co(1)OF5 octahedra, and corners with three equivalent Co(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. The Li(1)-F(2) bond length is 1.97 Å. The Li(1)-F(3) bond length is 1.99 Å. The Li(1)-F(4) bond length is 1.94 Å. The Li(1)-F(5) bond length is 1.94 Å. In the second Li site, Li(2) is bonded to one O(1), one F(1), one F(6), and one F(7) atom to form LiOF3 tetrahedra that share corners with three equivalent Li(4)F6 octahedra, corners with three equivalent Li(3)OF5 octahedra, corners with three equivalent Co(1)OF5 octahedra, and corners with three equivalent Co(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 53-61°. The Li(2)-O(1) bond length is 2.00 Å. The Li(2)-F(1) bond length is 1.94 Å. The Li(2)-F(6) bond length is 1.92 Å. The Li(2)-F(7) bond length is 1.94 Å. In the third Li site, Li(3) is bonded to one O(1), one F(3), one F(4), one F(5), one F(6), and one F(7) atom to form LiOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Co(1)OF5 octahedra, and edges with two equivalent Co(2)OF5 octahedra. The Li(3)-O(1) bond length is 2.13 Å. The Li(3)-F(3) bond length is 2.11 Å. The Li(3)-F(4) bond length is 2.02 Å. The Li(3)-F(5) bond length is 2.04 Å. The Li(3)-F(6) bond length is 2.09 Å. The Li(3)-F(7) bond length is 2.06 Å. In the fourth Li site, Li(4) is bonded to one F(1), one F(2), one F(4), one F(5), one F(6), and one F(7) atom to form LiF6 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with two equivalent Li(3)OF5 octahedra, edges with two equivalent Co(1)OF5 octahedra, and edges with two equivalent Co(2)OF5 octahedra. The Li(4)-F(1) bond length is 2.04 Å. The Li(4)-F(2) bond length is 2.10 Å. The Li(4)-F(4) bond length is 2.06 Å. The Li(4)-F(5) bond length is 2.04 Å. The Li(4)-F(6) bond length is 2.06 Å. The Li(4)-F(7) bond length is 2.03 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one F(1), one F(2), one F(3), one F(4), and one F(6) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(3)OF5 octahedra, and edges with two equivalent Co(2)OF5 octahedra. The Co(1)-O(1) bond length is 1.75 Å. The Co(1)-F(1) bond length is 2.09 Å. The Co(1)-F(2) bond length is 2.06 Å. The Co(1)-F(3) bond length is 2.09 Å. The Co(1)-F(4) bond length is 2.01 Å. The Co(1)-F(6) bond length is 2.01 Å. In the second Co site, Co(2) is bonded to one O(1), one F(1), one F(2), one F(3), one F(5), and one F(7) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(2)OF3 tetrahedra, edges with two equivalent Li(4)F6 octahedra, edges with two equivalent Li(3)OF5 octahedra, and edges with two equivalent Co(1)OF5 octahedra. The Co(2)-O(1) bond length is 1.97 Å. The Co(2)-F(1) bond length is 2.15 Å. The Co(2)-F(2) bond length is 2.09 Å. The Co(2)-F(3) bond length is 2.10 Å. The Co(2)-F(5) bond length is 2.03 Å. The Co(2)-F(7) bond length is 2.03 Å. O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(1), and one Co(2) atom. There are seven 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), one Co(1), and one Co(2) atom. In the second F site, F(2) is bonded to one Li(1), one Li(4), one Co(1), and one Co(2) atom to form a mixture of distorted corner and edge-sharing FLi2Co2 trigonal pyramids. In the third F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Co(1), and one Co(2) atom. In the fourth F site, F(4) is bonded to one Li(1), one Li(3), one Li(4), and one Co(1) atom to form a mixture of distorted corner and edge-sharing FLi3Co trigonal pyramids. In the fifth F site, F(5) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one Co(2) atom. In the sixth F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Co(1) atom. In the seventh F site, F(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one Co(2) atom.