LiV3(O2F)2 is Ilmenite-derived structured and crystallizes in the triclinic P1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one F(1), and one F(2) atom. 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 F(1), and one F(2) atom to form a mixture of distorted face and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-60°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form a mixture of edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-49°. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form a mixture of distorted edge, face, and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded to one Li(1), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share corners with four equivalent F(1)LiV3 trigonal pyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one V(1), one V(2), and one V(3) atom to form distorted FLiV3 trigonal pyramids that share corners with four equivalent O(4)LiV3 trigonal pyramids. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one V(3) atom.
LiV3(O2F)2 is Ilmenite-derived structured and crystallizes in the triclinic P1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one F(1), and one F(2) atom. The Li(1)-O(2) bond length is 2.03 Å. The Li(1)-O(3) bond length is 2.42 Å. The Li(1)-O(4) bond length is 2.15 Å. The Li(1)-F(1) bond length is 2.04 Å. The Li(1)-F(2) bond length is 2.04 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 F(1), and one F(2) atom to form a mixture of distorted face and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-60°. The V(1)-O(1) bond length is 2.01 Å. The V(1)-O(2) bond length is 2.00 Å. The V(1)-O(3) bond length is 1.97 Å. The V(1)-O(4) bond length is 1.94 Å. The V(1)-F(1) bond length is 2.30 Å. The V(1)-F(2) bond length is 2.27 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form a mixture of edge and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 35-49°. The V(2)-O(1) bond length is 1.94 Å. The V(2)-O(2) bond length is 2.00 Å. The V(2)-O(3) bond length is 2.04 Å. The V(2)-O(4) bond length is 2.03 Å. The V(2)-F(1) bond length is 2.14 Å. The V(2)-F(2) bond length is 2.14 Å. In the third V site, V(3) is bonded to one O(1), one O(2), one O(3), one O(4), one F(1), and one F(2) atom to form a mixture of distorted edge, face, and corner-sharing VO4F2 octahedra. The corner-sharing octahedral tilt angles range from 56-60°. The V(3)-O(1) bond length is 1.97 Å. The V(3)-O(2) bond length is 2.02 Å. The V(3)-O(3) bond length is 1.95 Å. The V(3)-O(4) bond length is 1.98 Å. The V(3)-F(1) bond length is 2.18 Å. The V(3)-F(2) bond length is 2.28 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one V(3) atom. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded to one Li(1), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share corners with four equivalent F(1)LiV3 trigonal pyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded to one Li(1), one V(1), one V(2), and one V(3) atom to form distorted FLiV3 trigonal pyramids that share corners with four equivalent O(4)LiV3 trigonal pyramids. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one V(3) atom.