Li4CoO3F is Aluminum carbonitride-derived structured and crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(6), and one F(2) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Li(4)O4F square pyramid,  a cornercorner with one Li(5)O4F square pyramid, corners with two equivalent Li(2)O2F2 tetrahedra, corners with two equivalent Li(7)O4 tetrahedra, corners with two equivalent Co(2)O3F tetrahedra,  a cornercorner with one Li(6)O3F trigonal pyramid, and corners with two equivalent Co(1)O3F trigonal pyramids. In the second Li site, Li(2) is bonded to one O(2), one O(3), one F(1), and one F(2) atom to form LiO2F2 tetrahedra that share  a cornercorner with one Li(4)O4F square pyramid,  a cornercorner with one Co(2)O3F tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with two equivalent Li(6)O3F trigonal pyramids, corners with three equivalent Co(1)O3F trigonal pyramids,  an edgeedge with one Li(4)O4F square pyramid, and  an edgeedge with one Li(5)O4F square pyramid. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), one O(5), and one F(1) atom. In the fourth Li site, Li(4) is bonded to one O(2), one O(3), one O(4), one O(5), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(2)O2F2 tetrahedra,  a cornercorner with one Li(1)O3F tetrahedra, corners with two equivalent Co(2)O3F tetrahedra,  a cornercorner with one Li(6)O3F trigonal pyramid,  a cornercorner with one Co(1)O3F trigonal pyramid, edges with two equivalent Li(5)O4F square pyramids,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra,  an edgeedge with one Li(6)O3F trigonal pyramid, and  an edgeedge with one Co(1)O3F trigonal pyramid. In the fifth Li site, Li(5) is bonded to one O(3), one O(4), one O(5), one O(6), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(1)O3F tetrahedra,  a cornercorner with one Li(7)O4 tetrahedra,  a cornercorner with one Co(2)O3F tetrahedra, corners with two equivalent Li(6)O3F trigonal pyramids, corners with two equivalent Co(1)O3F trigonal pyramids, edges with two equivalent Li(4)O4F square pyramids,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra,  an edgeedge with one Co(2)O3F tetrahedra, and  an edgeedge with one Li(6)O3F trigonal pyramid. In the sixth Li site, Li(6) is bonded to one O(3), one O(5), one O(6), and one F(1) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one Li(4)O4F square pyramid, corners with two equivalent Li(5)O4F square pyramids,  a cornercorner with one Li(1)O3F tetrahedra, corners with two equivalent Li(2)O2F2 tetrahedra, corners with two equivalent Co(2)O3F tetrahedra,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(5)O4F square pyramid,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one Co(1)O3F trigonal pyramid. In the seventh Li site, Li(7) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Li(5)O4F square pyramid, corners with two equivalent Li(1)O3F tetrahedra, corners with three equivalent Co(2)O3F tetrahedra,  a cornercorner with one Co(1)O3F trigonal pyramid,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(5)O4F square pyramid, and  an edgeedge with one Li(6)O3F trigonal pyramid. In the eighth Li site, Li(8) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(6), and one F(2) atom. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(3), and one F(1) atom to form distorted CoO3F trigonal pyramids that share  a cornercorner with one Li(4)O4F square pyramid, corners with two equivalent Li(5)O4F square pyramids,  a cornercorner with one Li(7)O4 tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with three equivalent Li(2)O2F2 tetrahedra,  an edgeedge with one Li(4)O4F square pyramid, and  an edgeedge with one Li(6)O3F trigonal pyramid. In the second Co site, Co(2) is bonded to one O(4), one O(5), one O(6), and one F(2) atom to form CoO3F tetrahedra that share  a cornercorner with one Li(5)O4F square pyramid, corners with two equivalent Li(4)O4F square pyramids,  a cornercorner with one Li(2)O2F2 tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with three equivalent Li(7)O4 tetrahedra, corners with two equivalent Li(6)O3F trigonal pyramids, and  an edgeedge with one Li(5)O4F square pyramid. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(7), one Li(8), and one Co(1) atom to form OLi3Co tetrahedra that share  a cornercorner with one O(3)Li5Co octahedra,  a cornercorner with one O(5)Li5Co octahedra, corners with three equivalent O(2)Li5Co octahedra, corners with three equivalent O(6)Li5Co octahedra,  a cornercorner with one O(4)Li4Co trigonal bipyramid, and  an edgeedge with one F(2)Li3Co tetrahedra. The corner-sharing octahedral tilt angles range from 55-61°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(8), and one Co(1) atom to form OLi5Co octahedra that share corners with two equivalent O(5)Li5Co octahedra, corners with three equivalent O(1)Li3Co tetrahedra, corners with three equivalent F(2)Li3Co tetrahedra,  an edgeedge with one O(6)Li5Co octahedra, edges with two equivalent O(3)Li5Co octahedra, and  an edgeedge with one O(4)Li4Co trigonal bipyramid. The corner-sharing octahedral tilt angles range from 18-21°. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Co(1) atom to form OLi5Co octahedra that share corners with two equivalent O(6)Li5Co octahedra,  a cornercorner with one O(1)Li3Co tetrahedra,  a cornercorner with one F(2)Li3Co tetrahedra,  a cornercorner with one O(4)Li4Co trigonal bipyramid, edges with two equivalent O(2)Li5Co octahedra, edges with two equivalent O(5)Li5Co octahedra, and  an edgeedge with one O(4)Li4Co trigonal bipyramid. The corner-sharing octahedral tilt angles range from 9-24°. In the fourth O site, O(4) is bonded to one Li(3), one Li(4), one Li(5), one Li(7), and one Co(2) atom to form OLi4Co trigonal bipyramids that share  a cornercorner with one O(3)Li5Co octahedra,  a cornercorner with one O(5)Li5Co octahedra,  a cornercorner with one O(6)Li5Co octahedra,  a cornercorner with one O(1)Li3Co tetrahedra,  a cornercorner with one F(2)Li3Co tetrahedra,  an edgeedge with one O(2)Li5Co octahedra,  an edgeedge with one O(3)Li5Co octahedra,  an edgeedge with one O(6)Li5Co octahedra, and edges with two equivalent O(5)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 16-68°. In the fifth O site, O(5) is bonded to one Li(3), one Li(4), one Li(5), one Li(6), one Li(7), and one Co(2) atom to form OLi5Co octahedra that share corners with two equivalent O(2)Li5Co octahedra,  a cornercorner with one O(1)Li3Co tetrahedra,  a cornercorner with one F(2)Li3Co tetrahedra,  a cornercorner with one O(4)Li4Co trigonal bipyramid, edges with two equivalent O(3)Li5Co octahedra, edges with two equivalent O(6)Li5Co octahedra, and edges with two equivalent O(4)Li4Co trigonal bipyramids. The corner-sharing octahedral tilt angles range from 18-21°. In the sixth O site, O(6) is bonded to one Li(1), one Li(5), one Li(6), one Li(7), one Li(8), and one Co(2) atom to form OLi5Co octahedra that share corners with two equivalent O(3)Li5Co octahedra, corners with three equivalent O(1)Li3Co tetrahedra, corners with three equivalent F(2)Li3Co tetrahedra,  a cornercorner with one O(4)Li4Co trigonal bipyramid,  an edgeedge with one O(2)Li5Co octahedra, edges with two equivalent O(5)Li5Co octahedra, and  an edgeedge with one O(4)Li4Co trigonal bipyramid. The corner-sharing octahedral tilt angles range from 9-24°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Co(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(8), and one Co(2) atom to form FLi3Co tetrahedra that share  a cornercorner with one O(3)Li5Co octahedra,  a cornercorner with one O(5)Li5Co octahedra, corners with three equivalent O(2)Li5Co octahedra, corners with three equivalent O(6)Li5Co octahedra,  a cornercorner with one O(4)Li4Co trigonal bipyramid, and  an edgeedge with one O(1)Li3Co tetrahedra. The corner-sharing octahedral tilt angles range from 56-70°.
Li4CoO3F is Aluminum carbonitride-derived structured and crystallizes in the triclinic P1 space group. There are eight inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(6), and one F(2) atom to form distorted LiO3F tetrahedra that share  a cornercorner with one Li(4)O4F square pyramid,  a cornercorner with one Li(5)O4F square pyramid, corners with two equivalent Li(2)O2F2 tetrahedra, corners with two equivalent Li(7)O4 tetrahedra, corners with two equivalent Co(2)O3F tetrahedra,  a cornercorner with one Li(6)O3F trigonal pyramid, and corners with two equivalent Co(1)O3F trigonal pyramids. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(2) bond length is 2.04 Å. The Li(1)-O(6) bond length is 2.00 Å. The Li(1)-F(2) bond length is 2.01 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), one F(1), and one F(2) atom to form LiO2F2 tetrahedra that share  a cornercorner with one Li(4)O4F square pyramid,  a cornercorner with one Co(2)O3F tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with two equivalent Li(6)O3F trigonal pyramids, corners with three equivalent Co(1)O3F trigonal pyramids,  an edgeedge with one Li(4)O4F square pyramid, and  an edgeedge with one Li(5)O4F square pyramid. The Li(2)-O(2) bond length is 1.95 Å. The Li(2)-O(3) bond length is 1.97 Å. The Li(2)-F(1) bond length is 1.92 Å. The Li(2)-F(2) bond length is 1.97 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), one O(5), and one F(1) atom. The Li(3)-O(2) bond length is 2.04 Å. The Li(3)-O(3) bond length is 2.00 Å. The Li(3)-O(4) bond length is 1.99 Å. The Li(3)-O(5) bond length is 2.07 Å. The Li(3)-F(1) bond length is 2.55 Å. In the fourth Li site, Li(4) is bonded to one O(2), one O(3), one O(4), one O(5), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(2)O2F2 tetrahedra,  a cornercorner with one Li(1)O3F tetrahedra, corners with two equivalent Co(2)O3F tetrahedra,  a cornercorner with one Li(6)O3F trigonal pyramid,  a cornercorner with one Co(1)O3F trigonal pyramid, edges with two equivalent Li(5)O4F square pyramids,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra,  an edgeedge with one Li(6)O3F trigonal pyramid, and  an edgeedge with one Co(1)O3F trigonal pyramid. The Li(4)-O(2) bond length is 2.26 Å. The Li(4)-O(3) bond length is 1.99 Å. The Li(4)-O(4) bond length is 1.95 Å. The Li(4)-O(5) bond length is 2.00 Å. The Li(4)-F(1) bond length is 2.42 Å. In the fifth Li site, Li(5) is bonded to one O(3), one O(4), one O(5), one O(6), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one Li(1)O3F tetrahedra,  a cornercorner with one Li(7)O4 tetrahedra,  a cornercorner with one Co(2)O3F tetrahedra, corners with two equivalent Li(6)O3F trigonal pyramids, corners with two equivalent Co(1)O3F trigonal pyramids, edges with two equivalent Li(4)O4F square pyramids,  an edgeedge with one Li(2)O2F2 tetrahedra,  an edgeedge with one Li(7)O4 tetrahedra,  an edgeedge with one Co(2)O3F tetrahedra, and  an edgeedge with one Li(6)O3F trigonal pyramid. The Li(5)-O(3) bond length is 2.04 Å. The Li(5)-O(4) bond length is 2.05 Å. The Li(5)-O(5) bond length is 2.07 Å. The Li(5)-O(6) bond length is 2.27 Å. The Li(5)-F(1) bond length is 1.99 Å. In the sixth Li site, Li(6) is bonded to one O(3), one O(5), one O(6), and one F(1) atom to form distorted LiO3F trigonal pyramids that share  a cornercorner with one Li(4)O4F square pyramid, corners with two equivalent Li(5)O4F square pyramids,  a cornercorner with one Li(1)O3F tetrahedra, corners with two equivalent Li(2)O2F2 tetrahedra, corners with two equivalent Co(2)O3F tetrahedra,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(5)O4F square pyramid,  an edgeedge with one Li(7)O4 tetrahedra, and  an edgeedge with one Co(1)O3F trigonal pyramid. The Li(6)-O(3) bond length is 2.03 Å. The Li(6)-O(5) bond length is 1.95 Å. The Li(6)-O(6) bond length is 2.13 Å. The Li(6)-F(1) bond length is 2.01 Å. In the seventh Li site, Li(7) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one Li(5)O4F square pyramid, corners with two equivalent Li(1)O3F tetrahedra, corners with three equivalent Co(2)O3F tetrahedra,  a cornercorner with one Co(1)O3F trigonal pyramid,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(5)O4F square pyramid, and  an edgeedge with one Li(6)O3F trigonal pyramid. The Li(7)-O(1) bond length is 2.01 Å. The Li(7)-O(4) bond length is 1.95 Å. The Li(7)-O(5) bond length is 1.97 Å. The Li(7)-O(6) bond length is 2.02 Å. In the eighth Li site, Li(8) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(6), and one F(2) atom. The Li(8)-O(1) bond length is 2.01 Å. The Li(8)-O(2) bond length is 2.03 Å. The Li(8)-O(6) bond length is 2.06 Å. The Li(8)-F(2) bond length is 2.17 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1), one O(2), one O(3), and one F(1) atom to form distorted CoO3F trigonal pyramids that share  a cornercorner with one Li(4)O4F square pyramid, corners with two equivalent Li(5)O4F square pyramids,  a cornercorner with one Li(7)O4 tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with three equivalent Li(2)O2F2 tetrahedra,  an edgeedge with one Li(4)O4F square pyramid, and  an edgeedge with one Li(6)O3F trigonal pyramid. The Co(1)-O(1) bond length is 1.77 Å. The Co(1)-O(2) bond length is 1.85 Å. The Co(1)-O(3) bond length is 1.87 Å. The Co(1)-F(1) bond length is 2.05 Å. In the second Co site, Co(2) is bonded to one O(4), one O(5), one O(6), and one F(2) atom to form CoO3F tetrahedra that share  a cornercorner with one Li(5)O4F square pyramid, corners with two equivalent Li(4)O4F square pyramids,  a cornercorner with one Li(2)O2F2 tetrahedra, corners with two equivalent Li(1)O3F tetrahedra, corners with three equivalent Li(7)O4 tetrahedra, corners with two equivalent Li(6)O3F trigonal pyramids, and  an edgeedge with one Li(5)O4F square pyramid. The Co(2)-O(4) bond length is 1.78 Å. The Co(2)-O(5) bond length is 1.91 Å. The Co(2)-O(6) bond length is 1.80 Å. The Co(2)-F(2) bond length is 2.07 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(7), one Li(8), and one Co(1) atom to form OLi3Co tetrahedra that share  a cornercorner with one O(3)Li5Co octahedra,  a cornercorner with one O(5)Li5Co octahedra, corners with three equivalent O(2)Li5Co octahedra, corners with three equivalent O(6)Li5Co octahedra,  a cornercorner with one O(4)Li4Co trigonal bipyramid, and  an edgeedge with one F(2)Li3Co tetrahedra. The corner-sharing octahedral tilt angles range from 55-61°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(8), and one Co(1) atom to form OLi5Co octahedra that share corners with two equivalent O(5)Li5Co octahedra, corners with three equivalent O(1)Li3Co tetrahedra, corners with three equivalent F(2)Li3Co tetrahedra,  an edgeedge with one O(6)Li5Co octahedra, edges with two equivalent O(3)Li5Co octahedra, and  an edgeedge with one O(4)Li4Co trigonal bipyramid. The corner-sharing octahedral tilt angles range from 18-21°. In the third O site, O(3) is bonded to one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Co(1) atom to form OLi5Co octahedra that share corners with two equivalent O(6)Li5Co octahedra,  a cornercorner with one O(1)Li3Co tetrahedra,  a cornercorner with one F(2)Li3Co tetrahedra,  a cornercorner with one O(4)Li4Co trigonal bipyramid, edges with two equivalent O(2)Li5Co octahedra, edges with two equivalent O(5)Li5Co octahedra, and  an edgeedge with one O(4)Li4Co trigonal bipyramid. The corner-sharing octahedral tilt angles range from 9-24°. In the fourth O site, O(4) is bonded to one Li(3), one Li(4), one Li(5), one Li(7), and one Co(2) atom to form OLi4Co trigonal bipyramids that share  a cornercorner with one O(3)Li5Co octahedra,  a cornercorner with one O(5)Li5Co octahedra,  a cornercorner with one O(6)Li5Co octahedra,  a cornercorner with one O(1)Li3Co tetrahedra,  a cornercorner with one F(2)Li3Co tetrahedra,  an edgeedge with one O(2)Li5Co octahedra,  an edgeedge with one O(3)Li5Co octahedra,  an edgeedge with one O(6)Li5Co octahedra, and edges with two equivalent O(5)Li5Co octahedra. The corner-sharing octahedral tilt angles range from 16-68°. In the fifth O site, O(5) is bonded to one Li(3), one Li(4), one Li(5), one Li(6), one Li(7), and one Co(2) atom to form OLi5Co octahedra that share corners with two equivalent O(2)Li5Co octahedra,  a cornercorner with one O(1)Li3Co tetrahedra,  a cornercorner with one F(2)Li3Co tetrahedra,  a cornercorner with one O(4)Li4Co trigonal bipyramid, edges with two equivalent O(3)Li5Co octahedra, edges with two equivalent O(6)Li5Co octahedra, and edges with two equivalent O(4)Li4Co trigonal bipyramids. The corner-sharing octahedral tilt angles range from 18-21°. In the sixth O site, O(6) is bonded to one Li(1), one Li(5), one Li(6), one Li(7), one Li(8), and one Co(2) atom to form OLi5Co octahedra that share corners with two equivalent O(3)Li5Co octahedra, corners with three equivalent O(1)Li3Co tetrahedra, corners with three equivalent F(2)Li3Co tetrahedra,  a cornercorner with one O(4)Li4Co trigonal bipyramid,  an edgeedge with one O(2)Li5Co octahedra, edges with two equivalent O(5)Li5Co octahedra, and  an edgeedge with one O(4)Li4Co trigonal bipyramid. The corner-sharing octahedral tilt angles range from 9-24°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 6-coordinate geometry to one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Co(1) atom. In the second F site, F(2) is bonded to one Li(1), one Li(2), one Li(8), and one Co(2) atom to form FLi3Co tetrahedra that share  a cornercorner with one O(3)Li5Co octahedra,  a cornercorner with one O(5)Li5Co octahedra, corners with three equivalent O(2)Li5Co octahedra, corners with three equivalent O(6)Li5Co octahedra,  a cornercorner with one O(4)Li4Co trigonal bipyramid, and  an edgeedge with one O(1)Li3Co tetrahedra. The corner-sharing octahedral tilt angles range from 56-70°.