Li3Co3OF7 is Spinel-derived structured and crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), one F(5), and one F(6) atom to form LiF4 tetrahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Co(1)OF5 octahedra, corners with three equivalent Co(2)OF5 octahedra, and corners with three equivalent Co(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 56-61°. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(7) atom to form LiF6 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Co(1)OF5 octahedra, edges with two equivalent Co(2)OF5 octahedra, and edges with two equivalent Co(3)OF5 octahedra. In the third Li site, Li(3) is bonded to one O(1), one F(2), one F(3), and one F(7) atom to form LiOF3 tetrahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Co(1)OF5 octahedra, corners with three equivalent Co(2)OF5 octahedra, and corners with three equivalent Co(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one F(1), one F(2), one F(5), one F(6), and one F(7) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Co(2)OF5 octahedra, and edges with two equivalent Co(3)OF5 octahedra. In the second Co site, Co(2) is bonded to one O(1), one F(1), one F(3), one F(4), one F(6), and one F(7) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Co(1)OF5 octahedra, and edges with two equivalent Co(3)OF5 octahedra. In the third Co site, Co(3) is bonded to one O(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Co(1)OF5 octahedra, and edges with two equivalent Co(2)OF5 octahedra. O(1) is bonded to one Li(3), one Co(1), one Co(2), and one Co(3) atom to form distorted OLiCo3 trigonal pyramids that share corners with two equivalent F(4)Li2Co2 trigonal pyramids. There are seven inequivalent F sites. In the first F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Co(1), and one Co(3) atom. In the second F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(1), one Co(2), and one Co(3) atom. In the third F site, F(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(1), and one Co(2) atom. In the fourth F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Co(1), and one Co(2) atom. In the fifth F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(1), and one Co(3) atom. In the sixth F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(2), and one Co(3) atom. In the seventh F site, F(4) is bonded to one Li(1), one Li(2), one Co(2), and one Co(3) atom to form distorted FLi2Co2 trigonal pyramids that share corners with two equivalent O(1)LiCo3 trigonal pyramids.
Li3Co3OF7 is Spinel-derived structured and crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1), one F(4), one F(5), and one F(6) atom to form LiF4 tetrahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Co(1)OF5 octahedra, corners with three equivalent Co(2)OF5 octahedra, and corners with three equivalent Co(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 56-61°. The Li(1)-F(1) bond length is 1.97 Å. The Li(1)-F(4) bond length is 1.97 Å. The Li(1)-F(5) bond length is 1.96 Å. The Li(1)-F(6) bond length is 2.03 Å. In the second Li site, Li(2) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(7) atom to form LiF6 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Co(1)OF5 octahedra, edges with two equivalent Co(2)OF5 octahedra, and edges with two equivalent Co(3)OF5 octahedra. The Li(2)-F(1) bond length is 2.10 Å. The Li(2)-F(2) bond length is 2.06 Å. The Li(2)-F(3) bond length is 2.06 Å. The Li(2)-F(4) bond length is 2.07 Å. The Li(2)-F(5) bond length is 2.07 Å. The Li(2)-F(7) bond length is 2.03 Å. In the third Li site, Li(3) is bonded to one O(1), one F(2), one F(3), and one F(7) atom to form LiOF3 tetrahedra that share corners with three equivalent Li(2)F6 octahedra, corners with three equivalent Co(1)OF5 octahedra, corners with three equivalent Co(2)OF5 octahedra, and corners with three equivalent Co(3)OF5 octahedra. The corner-sharing octahedral tilt angles range from 52-59°. The Li(3)-O(1) bond length is 1.93 Å. The Li(3)-F(2) bond length is 1.98 Å. The Li(3)-F(3) bond length is 1.98 Å. The Li(3)-F(7) bond length is 1.96 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one F(1), one F(2), one F(5), one F(6), and one F(7) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Co(2)OF5 octahedra, and edges with two equivalent Co(3)OF5 octahedra. The Co(1)-O(1) bond length is 1.96 Å. The Co(1)-F(1) bond length is 2.11 Å. The Co(1)-F(2) bond length is 2.12 Å. The Co(1)-F(5) bond length is 2.10 Å. The Co(1)-F(6) bond length is 2.14 Å. The Co(1)-F(7) bond length is 2.11 Å. In the second Co site, Co(2) is bonded to one O(1), one F(1), one F(3), one F(4), one F(6), and one F(7) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Co(1)OF5 octahedra, and edges with two equivalent Co(3)OF5 octahedra. The Co(2)-O(1) bond length is 1.96 Å. The Co(2)-F(1) bond length is 2.07 Å. The Co(2)-F(3) bond length is 2.12 Å. The Co(2)-F(4) bond length is 2.09 Å. The Co(2)-F(6) bond length is 2.18 Å. The Co(2)-F(7) bond length is 2.11 Å. In the third Co site, Co(3) is bonded to one O(1), one F(2), one F(3), one F(4), one F(5), and one F(6) atom to form CoOF5 octahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Li(3)OF3 tetrahedra, edges with two equivalent Li(2)F6 octahedra, edges with two equivalent Co(1)OF5 octahedra, and edges with two equivalent Co(2)OF5 octahedra. The Co(3)-O(1) bond length is 1.96 Å. The Co(3)-F(2) bond length is 2.12 Å. The Co(3)-F(3) bond length is 2.11 Å. The Co(3)-F(4) bond length is 2.10 Å. The Co(3)-F(5) bond length is 2.11 Å. The Co(3)-F(6) bond length is 2.14 Å. O(1) is bonded to one Li(3), one Co(1), one Co(2), and one Co(3) atom to form distorted OLiCo3 trigonal pyramids that share corners with two equivalent F(4)Li2Co2 trigonal pyramids. There are seven inequivalent F sites. In the first F site, F(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Co(1), and one Co(3) atom. In the second F site, F(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Co(1), one Co(2), and one Co(3) atom. In the third F site, F(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(1), and one Co(2) atom. In the fourth F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Co(1), and one Co(2) atom. In the fifth F site, F(2) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(1), and one Co(3) atom. In the sixth F site, F(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Co(2), and one Co(3) atom. In the seventh F site, F(4) is bonded to one Li(1), one Li(2), one Co(2), and one Co(3) atom to form distorted FLi2Co2 trigonal pyramids that share corners with two equivalent O(1)LiCo3 trigonal pyramids.