Li3V2(O2F)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), one O(5), one F(1), one F(2), and one F(3) atom. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form edge-sharing LiF6 octahedra. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one O(4), one O(5), one F(1), one F(2), and one F(3) atom. In the fourth Li site, Li(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. In the fifth Li site, Li(5) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form edge-sharing LiF6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(4), one V(1), one V(2), and one V(3) atom to form a mixture of corner and edge-sharing OLi2V3 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), one V(1), one V(2), and one V(3) atom to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(3)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  a cornercorner with one O(6)Li2V3 square pyramid, corners with two equivalent F(2)Li5 square pyramids, corners with two equivalent F(3)Li5 square pyramids,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(6)Li2V3 square pyramid,  an edgeedge with one F(1)Li5 square pyramid, edges with two equivalent O(4)Li2V3 square pyramids, and edges with two equivalent O(5)Li2V3 square pyramids. In the third O site, O(3) is bonded to two equivalent Li(4), one V(1), one V(2), and one V(3) atom to form a mixture of corner and edge-sharing OLi2V3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(1), one V(2), and one V(3) atom to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid,  a cornercorner with one O(3)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  a cornercorner with one O(6)Li2V3 square pyramid, corners with two equivalent F(1)Li5 square pyramids, corners with two equivalent F(3)Li5 square pyramids,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(6)Li2V3 square pyramid,  an edgeedge with one F(2)Li5 square pyramid, edges with two equivalent O(2)Li2V3 square pyramids, and edges with two equivalent O(5)Li2V3 square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one V(1), one V(2), and one V(3) atom to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid,  a cornercorner with one O(3)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(6)Li2V3 square pyramid, corners with two equivalent F(1)Li5 square pyramids, corners with two equivalent F(2)Li5 square pyramids,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(6)Li2V3 square pyramid,  an edgeedge with one F(3)Li5 square pyramid, edges with two equivalent O(2)Li2V3 square pyramids, and edges with two equivalent O(4)Li2V3 square pyramids. In the sixth O site, O(6) is bonded to two equivalent Li(4), one V(1), one V(2), and one V(3) atom to form a mixture of corner and edge-sharing OLi2V3 square pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(3), one Li(5), and two equivalent Li(2) atoms to form FLi5 square pyramids that share  a cornercorner with one F(1)Li5 square pyramid, corners with two equivalent O(4)Li2V3 square pyramids, corners with two equivalent O(5)Li2V3 square pyramids, corners with two equivalent F(2)Li5 square pyramids, corners with two equivalent F(3)Li5 square pyramids,  an edgeedge with one O(2)Li2V3 square pyramid,  an edgeedge with one F(1)Li5 square pyramid, edges with three equivalent F(2)Li5 square pyramids, and edges with three equivalent F(3)Li5 square pyramids. In the second F site, F(2) is bonded to one Li(1), one Li(3), one Li(5), and two equivalent Li(2) atoms to form FLi5 square pyramids that share  a cornercorner with one F(2)Li5 square pyramid, corners with two equivalent O(2)Li2V3 square pyramids, corners with two equivalent O(5)Li2V3 square pyramids, corners with two equivalent F(1)Li5 square pyramids, corners with two equivalent F(3)Li5 square pyramids,  an edgeedge with one O(4)Li2V3 square pyramid,  an edgeedge with one F(2)Li5 square pyramid, edges with three equivalent F(1)Li5 square pyramids, and edges with three equivalent F(3)Li5 square pyramids. In the third F site, F(3) is bonded to one Li(1), one Li(3), one Li(5), and two equivalent Li(2) atoms to form FLi5 square pyramids that share  a cornercorner with one F(3)Li5 square pyramid, corners with two equivalent O(2)Li2V3 square pyramids, corners with two equivalent O(4)Li2V3 square pyramids, corners with two equivalent F(1)Li5 square pyramids, corners with two equivalent F(2)Li5 square pyramids,  an edgeedge with one O(5)Li2V3 square pyramid,  an edgeedge with one F(3)Li5 square pyramid, edges with three equivalent F(1)Li5 square pyramids, and edges with three equivalent F(2)Li5 square pyramids.
Li3V2(O2F)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(4), one O(5), one F(1), one F(2), and one F(3) atom. The Li(1)-O(2) bond length is 2.50 Å. The Li(1)-O(4) bond length is 2.46 Å. The Li(1)-O(5) bond length is 2.55 Å. The Li(1)-F(1) bond length is 1.89 Å. The Li(1)-F(2) bond length is 1.89 Å. The Li(1)-F(3) bond length is 1.91 Å. In the second Li site, Li(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form edge-sharing LiF6 octahedra. There is one shorter (2.03 Å) and one longer (2.16 Å) Li(2)-F(1) bond length. There is one shorter (2.04 Å) and one longer (2.16 Å) Li(2)-F(2) bond length. There is one shorter (2.04 Å) and one longer (2.05 Å) Li(2)-F(3) bond length. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(2), one O(4), one O(5), one F(1), one F(2), and one F(3) atom. The Li(3)-O(2) bond length is 2.49 Å. The Li(3)-O(4) bond length is 2.56 Å. The Li(3)-O(5) bond length is 2.46 Å. The Li(3)-F(1) bond length is 1.89 Å. The Li(3)-F(2) bond length is 1.89 Å. The Li(3)-F(3) bond length is 1.91 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. There is one shorter (2.17 Å) and one longer (2.18 Å) Li(4)-O(1) bond length. There is one shorter (2.16 Å) and one longer (2.23 Å) Li(4)-O(3) bond length. There is one shorter (2.15 Å) and one longer (2.21 Å) Li(4)-O(6) bond length. In the fifth Li site, Li(5) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form edge-sharing LiF6 octahedra. Both Li(5)-F(1) bond lengths are 2.13 Å. Both Li(5)-F(2) bond lengths are 2.12 Å. Both Li(5)-F(3) bond lengths are 1.98 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. The V(1)-O(1) bond length is 1.94 Å. The V(1)-O(2) bond length is 1.88 Å. The V(1)-O(3) bond length is 2.06 Å. The V(1)-O(4) bond length is 1.98 Å. The V(1)-O(5) bond length is 1.97 Å. The V(1)-O(6) bond length is 2.05 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. The V(2)-O(1) bond length is 2.09 Å. The V(2)-O(2) bond length is 2.02 Å. The V(2)-O(3) bond length is 2.00 Å. The V(2)-O(4) bond length is 2.01 Å. The V(2)-O(5) bond length is 2.00 Å. The V(2)-O(6) bond length is 2.06 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 9°. The V(3)-O(1) bond length is 2.06 Å. The V(3)-O(2) bond length is 2.03 Å. The V(3)-O(3) bond length is 2.05 Å. The V(3)-O(4) bond length is 1.98 Å. The V(3)-O(5) bond length is 2.01 Å. The V(3)-O(6) bond length is 2.02 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(4), one V(1), one V(2), and one V(3) atom to form a mixture of corner and edge-sharing OLi2V3 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), one V(1), one V(2), and one V(3) atom to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(3)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  a cornercorner with one O(6)Li2V3 square pyramid, corners with two equivalent F(2)Li5 square pyramids, corners with two equivalent F(3)Li5 square pyramids,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(6)Li2V3 square pyramid,  an edgeedge with one F(1)Li5 square pyramid, edges with two equivalent O(4)Li2V3 square pyramids, and edges with two equivalent O(5)Li2V3 square pyramids. In the third O site, O(3) is bonded to two equivalent Li(4), one V(1), one V(2), and one V(3) atom to form a mixture of corner and edge-sharing OLi2V3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(1), one V(2), and one V(3) atom to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid,  a cornercorner with one O(3)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  a cornercorner with one O(6)Li2V3 square pyramid, corners with two equivalent F(1)Li5 square pyramids, corners with two equivalent F(3)Li5 square pyramids,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(6)Li2V3 square pyramid,  an edgeedge with one F(2)Li5 square pyramid, edges with two equivalent O(2)Li2V3 square pyramids, and edges with two equivalent O(5)Li2V3 square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one V(1), one V(2), and one V(3) atom to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid,  a cornercorner with one O(3)Li2V3 square pyramid,  a cornercorner with one O(4)Li2V3 square pyramid,  a cornercorner with one O(6)Li2V3 square pyramid, corners with two equivalent F(1)Li5 square pyramids, corners with two equivalent F(2)Li5 square pyramids,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(3)Li2V3 square pyramid,  an edgeedge with one O(6)Li2V3 square pyramid,  an edgeedge with one F(3)Li5 square pyramid, edges with two equivalent O(2)Li2V3 square pyramids, and edges with two equivalent O(4)Li2V3 square pyramids. In the sixth O site, O(6) is bonded to two equivalent Li(4), one V(1), one V(2), and one V(3) atom to form a mixture of corner and edge-sharing OLi2V3 square pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one Li(3), one Li(5), and two equivalent Li(2) atoms to form FLi5 square pyramids that share  a cornercorner with one F(1)Li5 square pyramid, corners with two equivalent O(4)Li2V3 square pyramids, corners with two equivalent O(5)Li2V3 square pyramids, corners with two equivalent F(2)Li5 square pyramids, corners with two equivalent F(3)Li5 square pyramids,  an edgeedge with one O(2)Li2V3 square pyramid,  an edgeedge with one F(1)Li5 square pyramid, edges with three equivalent F(2)Li5 square pyramids, and edges with three equivalent F(3)Li5 square pyramids. In the second F site, F(2) is bonded to one Li(1), one Li(3), one Li(5), and two equivalent Li(2) atoms to form FLi5 square pyramids that share  a cornercorner with one F(2)Li5 square pyramid, corners with two equivalent O(2)Li2V3 square pyramids, corners with two equivalent O(5)Li2V3 square pyramids, corners with two equivalent F(1)Li5 square pyramids, corners with two equivalent F(3)Li5 square pyramids,  an edgeedge with one O(4)Li2V3 square pyramid,  an edgeedge with one F(2)Li5 square pyramid, edges with three equivalent F(1)Li5 square pyramids, and edges with three equivalent F(3)Li5 square pyramids. In the third F site, F(3) is bonded to one Li(1), one Li(3), one Li(5), and two equivalent Li(2) atoms to form FLi5 square pyramids that share  a cornercorner with one F(3)Li5 square pyramid, corners with two equivalent O(2)Li2V3 square pyramids, corners with two equivalent O(4)Li2V3 square pyramids, corners with two equivalent F(1)Li5 square pyramids, corners with two equivalent F(2)Li5 square pyramids,  an edgeedge with one O(5)Li2V3 square pyramid,  an edgeedge with one F(3)Li5 square pyramid, edges with three equivalent F(1)Li5 square pyramids, and edges with three equivalent F(2)Li5 square pyramids.