Li4VO4F crystallizes in the monoclinic P2_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one F(1) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one F(1) atom. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), one O(4), and one F(1) atom. In the fourth Li site, Li(4) is bonded to one O(1), one O(3), one O(4), and one F(1) atom to form distorted LiO3F tetrahedra that share corners with three equivalent V(1)O4 tetrahedra. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with three equivalent Li(4)O3F tetrahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one V(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one V(1) atom. In the third O site, O(3) is bonded in a distorted trigonal bipyramidal geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Li(4), and one V(1) atom. F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Li(4) atom.
Li4VO4F crystallizes in the monoclinic P2_1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one F(1) atom. The Li(1)-O(2) bond length is 2.03 Å. The Li(1)-O(3) bond length is 2.14 Å. The Li(1)-O(4) bond length is 1.97 Å. The Li(1)-F(1) bond length is 1.88 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one F(1) atom. The Li(2)-O(1) bond length is 2.06 Å. The Li(2)-O(2) bond length is 1.98 Å. The Li(2)-O(3) bond length is 2.06 Å. The Li(2)-F(1) bond length is 1.83 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), one O(4), and one F(1) atom. The Li(3)-O(1) bond length is 2.04 Å. The Li(3)-O(3) bond length is 2.03 Å. The Li(3)-O(4) bond length is 1.98 Å. The Li(3)-F(1) bond length is 1.87 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(3), one O(4), and one F(1) atom to form distorted LiO3F tetrahedra that share corners with three equivalent V(1)O4 tetrahedra. The Li(4)-O(1) bond length is 2.02 Å. The Li(4)-O(3) bond length is 2.01 Å. The Li(4)-O(4) bond length is 2.10 Å. The Li(4)-F(1) bond length is 1.85 Å. V(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form VO4 tetrahedra that share corners with three equivalent Li(4)O3F tetrahedra. The V(1)-O(1) bond length is 1.75 Å. The V(1)-O(2) bond length is 1.72 Å. The V(1)-O(3) bond length is 1.75 Å. The V(1)-O(4) bond length is 1.77 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one V(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one V(1) atom. In the third O site, O(3) is bonded in a distorted trigonal bipyramidal geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Li(4), and one V(1) atom. F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(3), and one Li(4) atom.