K3V2P2O8F3 crystallizes in the orthorhombic Cmc2_1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to two equivalent O(2), two equivalent O(3), one F(1), and two equivalent F(2) atoms. In the second K site, K(2) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(4), one F(1), and two equivalent F(2) atoms. In the third K site, K(3) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(3), one F(1), and two equivalent F(2) atoms. 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  a cornercorner with one V(1)O4F2 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 2°. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with four equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 39-42°. There are four inequivalent O sites. In the first O site, O(2) is bonded in a 3-coordinate geometry to one K(1), one V(1), and one P(1) atom. In the second O site, O(3) is bonded in a 4-coordinate geometry to one K(1), one K(3), one V(1), and one P(1) atom. In the third O site, O(4) is bonded in a 3-coordinate geometry to one K(2), one V(1), and one P(1) atom. In the fourth O site, O(1) is bonded in a 4-coordinate geometry to one K(2), one K(3), one V(1), and one P(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one K(1), one K(2), one K(3), and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one K(2), one K(3), and one V(1) atom.
K3V2P2O8F3 crystallizes in the orthorhombic Cmc2_1 space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to two equivalent O(2), two equivalent O(3), one F(1), and two equivalent F(2) atoms. Both K(1)-O(2) bond lengths are 2.75 Å. Both K(1)-O(3) bond lengths are 2.66 Å. The K(1)-F(1) bond length is 2.65 Å. Both K(1)-F(2) bond lengths are 2.67 Å. In the second K site, K(2) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(4), one F(1), and two equivalent F(2) atoms. Both K(2)-O(1) bond lengths are 2.99 Å. Both K(2)-O(4) bond lengths are 2.65 Å. The K(2)-F(1) bond length is 3.18 Å. Both K(2)-F(2) bond lengths are 2.61 Å. In the third K site, K(3) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(3), one F(1), and two equivalent F(2) atoms. Both K(3)-O(1) bond lengths are 2.68 Å. Both K(3)-O(3) bond lengths are 2.87 Å. The K(3)-F(1) bond length is 2.67 Å. Both K(3)-F(2) bond lengths are 2.63 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  a cornercorner with one V(1)O4F2 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 2°. The V(1)-O(1) bond length is 2.03 Å. The V(1)-O(2) bond length is 2.05 Å. The V(1)-O(3) bond length is 2.08 Å. The V(1)-O(4) bond length is 1.99 Å. The V(1)-F(1) bond length is 2.16 Å. The V(1)-F(2) bond length is 2.00 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with four equivalent V(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 39-42°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.56 Å. There are four inequivalent O sites. In the first O site, O(2) is bonded in a 3-coordinate geometry to one K(1), one V(1), and one P(1) atom. In the second O site, O(3) is bonded in a 4-coordinate geometry to one K(1), one K(3), one V(1), and one P(1) atom. In the third O site, O(4) is bonded in a 3-coordinate geometry to one K(2), one V(1), and one P(1) atom. In the fourth O site, O(1) is bonded in a 4-coordinate geometry to one K(2), one K(3), one V(1), and one P(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one K(1), one K(2), one K(3), and two equivalent V(1) atoms. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one K(2), one K(3), and one V(1) atom.