VPO4F crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a distorted hexagonal planar geometry to two equivalent P(1), two equivalent O(1), and two equivalent O(4) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to two equivalent P(1), two equivalent O(3), and two equivalent F(1) atoms. P(1) is bonded in a 4-coordinate geometry to one V(1), one V(2), one O(1), and one O(3) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one F(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2), one P(1), and one O(3) atom. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one V(1) and one F(1) atom. F(1) is bonded in a distorted water-like geometry to one V(2), one O(2), and one O(4) atom.
VPO4F crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded in a distorted hexagonal planar geometry to two equivalent P(1), two equivalent O(1), and two equivalent O(4) atoms. Both V(1)-P(1) bond lengths are 2.18 Å. Both V(1)-O(1) bond lengths are 2.58 Å. Both V(1)-O(4) bond lengths are 2.71 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to two equivalent P(1), two equivalent O(3), and two equivalent F(1) atoms. Both V(2)-P(1) bond lengths are 2.27 Å. Both V(2)-O(3) bond lengths are 2.29 Å. Both V(2)-F(1) bond lengths are 2.80 Å. P(1) is bonded in a 4-coordinate geometry to one V(1), one V(2), one O(1), and one O(3) atom. The P(1)-O(1) bond length is 1.46 Å. The P(1)-O(3) bond length is 1.95 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one F(1) atom. The O(2)-F(1) bond length is 1.17 Å. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(2), one P(1), and one O(3) atom. The O(3)-O(3) bond length is 1.70 Å. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one V(1) and one F(1) atom. The O(4)-F(1) bond length is 1.63 Å. F(1) is bonded in a distorted water-like geometry to one V(2), one O(2), and one O(4) atom.