Li5VO4F crystallizes in the monoclinic P2_1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. In the second Li site, Li(2) 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 third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO4F trigonal bipyramids. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO4F square pyramids. In the fifth Li site, Li(5) is bonded in a distorted see-saw-like geometry to one O(1), one O(3), one O(4), and one F(1) atom. V(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one F(1) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and one V(1) atom to form a mixture of corner and edge-sharing OLi4V trigonal bipyramids. The corner-sharing octahedral tilt angles are 29°. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom to form a mixture of corner and edge-sharing OLi5V octahedra. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom. F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom.
Li5VO4F crystallizes in the monoclinic P2_1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Li(1)-O(1) bond length is 2.01 Å. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(3) bond length is 2.09 Å. The Li(1)-O(4) bond length is 2.02 Å. In the second Li site, Li(2) 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(2)-O(2) bond length is 1.99 Å. The Li(2)-O(3) bond length is 2.09 Å. The Li(2)-O(4) bond length is 2.00 Å. The Li(2)-F(1) bond length is 1.87 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO4F trigonal bipyramids. The Li(3)-O(1) bond length is 2.06 Å. The Li(3)-O(2) bond length is 1.97 Å. The Li(3)-O(3) bond length is 2.09 Å. The Li(3)-O(4) bond length is 2.35 Å. The Li(3)-F(1) bond length is 1.92 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), and one F(1) atom to form a mixture of distorted corner and edge-sharing LiO4F square pyramids. The Li(4)-O(1) bond length is 2.03 Å. The Li(4)-O(2) bond length is 2.34 Å. The Li(4)-O(3) bond length is 2.05 Å. The Li(4)-O(4) bond length is 2.13 Å. The Li(4)-F(1) bond length is 2.08 Å. In the fifth Li site, Li(5) is bonded in a distorted see-saw-like geometry to one O(1), one O(3), one O(4), and one F(1) atom. The Li(5)-O(1) bond length is 2.00 Å. The Li(5)-O(3) bond length is 2.01 Å. The Li(5)-O(4) bond length is 2.01 Å. The Li(5)-F(1) bond length is 1.88 Å. V(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), one O(4), and one F(1) atom. The V(1)-O(1) bond length is 1.82 Å. The V(1)-O(2) bond length is 1.82 Å. The V(1)-O(3) bond length is 1.89 Å. The V(1)-O(4) bond length is 1.85 Å. The V(1)-F(1) bond length is 2.55 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), and one V(1) atom to form a mixture of corner and edge-sharing OLi4V trigonal bipyramids. The corner-sharing octahedral tilt angles are 29°. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), and one V(1) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom to form a mixture of corner and edge-sharing OLi5V octahedra. In the fourth O site, O(4) is bonded in a 6-coordinate geometry to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom. F(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), one Li(5), and one V(1) atom.