Li2VPO4F is Hausmannite-derived structured and crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), two equivalent O(1), and one F(1) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), one F(1), and one F(2) atom. 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 VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-64°. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 41-47°. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-46°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one P(2) atom to form distorted OLi2VP tetrahedra that share  a cornercorner with one O(2)Li2VP tetrahedra,  a cornercorner with one O(4)Li2VP trigonal pyramid, corners with two equivalent F(2)Li2V2 trigonal pyramids, and edges with two equivalent O(4)Li2VP trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), and one P(2) atom to form distorted OLi2VP trigonal pyramids that share  a cornercorner with one O(2)Li2VP tetrahedra,  a cornercorner with one O(4)Li2VP trigonal pyramid, corners with two equivalent F(2)Li2V2 trigonal pyramids, and edges with two equivalent O(2)Li2VP tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent V(1) atoms. In the second F site, F(2) is bonded to two equivalent Li(2) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with four equivalent O(2)Li2VP tetrahedra and corners with four equivalent O(4)Li2VP trigonal pyramids.
Li2VPO4F is Hausmannite-derived structured and crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), two equivalent O(1), and one F(1) atom. The Li(1)-O(2) bond length is 2.27 Å. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(4) bond length is 2.09 Å. There is one shorter (2.14 Å) and one longer (2.53 Å) Li(1)-O(1) bond length. The Li(1)-F(1) bond length is 2.16 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), one F(1), and one F(2) atom. The Li(2)-O(2) bond length is 1.99 Å. The Li(2)-O(3) bond length is 2.01 Å. The Li(2)-O(4) bond length is 2.00 Å. The Li(2)-F(1) bond length is 2.50 Å. The Li(2)-F(2) bond length is 1.92 Å. 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 VO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-64°. The V(1)-O(1) bond length is 2.17 Å. The V(1)-O(2) bond length is 2.18 Å. The V(1)-O(3) bond length is 2.15 Å. The V(1)-O(4) bond length is 2.15 Å. The V(1)-F(1) bond length is 2.19 Å. The V(1)-F(2) bond length is 2.13 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 41-47°. Both P(1)-O(1) bond lengths are 1.55 Å. Both P(1)-O(3) bond lengths are 1.56 Å. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-46°. Both P(2)-O(2) bond lengths are 1.56 Å. Both P(2)-O(4) bond lengths are 1.55 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and one P(2) atom to form distorted OLi2VP tetrahedra that share  a cornercorner with one O(2)Li2VP tetrahedra,  a cornercorner with one O(4)Li2VP trigonal pyramid, corners with two equivalent F(2)Li2V2 trigonal pyramids, and edges with two equivalent O(4)Li2VP trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), and one P(2) atom to form distorted OLi2VP trigonal pyramids that share  a cornercorner with one O(2)Li2VP tetrahedra,  a cornercorner with one O(4)Li2VP trigonal pyramid, corners with two equivalent F(2)Li2V2 trigonal pyramids, and edges with two equivalent O(2)Li2VP tetrahedra. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 6-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and two equivalent V(1) atoms. In the second F site, F(2) is bonded to two equivalent Li(2) and two equivalent V(1) atoms to form distorted FLi2V2 trigonal pyramids that share corners with four equivalent O(2)Li2VP tetrahedra and corners with four equivalent O(4)Li2VP trigonal pyramids.