LiV2O2F3 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a 6-coordinate geometry to one F(3), two equivalent F(1), and three equivalent F(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), three equivalent O(2), and one F(3) atom to form distorted VO5F octahedra that share  a cornercorner with one V(2)O2F4 octahedra, corners with two equivalent V(1)O5F octahedra, edges with three equivalent V(2)O2F4 octahedra, and edges with three equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 21-34°. In the second V site, V(2) is bonded to one O(1), one O(2), one F(1), one F(2), and two equivalent F(3) atoms to form VO2F4 octahedra that share  a cornercorner with one V(1)O5F octahedra, corners with two equivalent V(2)O2F4 octahedra, and edges with three equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 21-28°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded to one V(2) and three equivalent V(1) atoms to form OV4 trigonal pyramids that share  a cornercorner with one F(2)Li3V trigonal pyramid, corners with two equivalent O(2)V4 trigonal pyramids, and edges with two equivalent O(2)V4 trigonal pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one V(2) atom. In the second F site, F(2) is bonded to three equivalent Li(1) and one V(2) atom to form FLi3V trigonal pyramids that share  a cornercorner with one O(2)V4 trigonal pyramid, corners with two equivalent F(2)Li3V trigonal pyramids, and edges with two equivalent F(2)Li3V trigonal pyramids. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one V(1), and two equivalent V(2) atoms.
LiV2O2F3 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a 6-coordinate geometry to one F(3), two equivalent F(1), and three equivalent F(2) atoms. The Li(1)-F(3) bond length is 2.47 Å. There is one shorter (1.92 Å) and one longer (1.95 Å) Li(1)-F(1) bond length. There are two shorter (2.11 Å) and one longer (2.34 Å) Li(1)-F(2) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), three equivalent O(2), and one F(3) atom to form distorted VO5F octahedra that share  a cornercorner with one V(2)O2F4 octahedra, corners with two equivalent V(1)O5F octahedra, edges with three equivalent V(2)O2F4 octahedra, and edges with three equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 21-34°. There is one shorter (1.91 Å) and one longer (2.01 Å) V(1)-O(1) bond length. There are two shorter (2.07 Å) and one longer (2.15 Å) V(1)-O(2) bond length. The V(1)-F(3) bond length is 2.25 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one F(1), one F(2), and two equivalent F(3) atoms to form VO2F4 octahedra that share  a cornercorner with one V(1)O5F octahedra, corners with two equivalent V(2)O2F4 octahedra, and edges with three equivalent V(1)O5F octahedra. The corner-sharing octahedral tilt angles range from 21-28°. The V(2)-O(1) bond length is 1.94 Å. The V(2)-O(2) bond length is 2.05 Å. The V(2)-F(1) bond length is 1.96 Å. The V(2)-F(2) bond length is 2.00 Å. Both V(2)-F(3) bond lengths are 2.04 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one V(2) and two equivalent V(1) atoms. In the second O site, O(2) is bonded to one V(2) and three equivalent V(1) atoms to form OV4 trigonal pyramids that share  a cornercorner with one F(2)Li3V trigonal pyramid, corners with two equivalent O(2)V4 trigonal pyramids, and edges with two equivalent O(2)V4 trigonal pyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one V(2) atom. In the second F site, F(2) is bonded to three equivalent Li(1) and one V(2) atom to form FLi3V trigonal pyramids that share  a cornercorner with one O(2)V4 trigonal pyramid, corners with two equivalent F(2)Li3V trigonal pyramids, and edges with two equivalent F(2)Li3V trigonal pyramids. In the third F site, F(3) is bonded in a 4-coordinate geometry to one Li(1), one V(1), and two equivalent V(2) atoms.