K2V3P2O13F2 crystallizes in the triclinic P-1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to one O(11), one O(12), one O(5), one O(6), one O(8), one O(9), two equivalent O(10), one F(1), and one F(2) atom. In the second K site, K(2) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(11), one O(13), one O(2), one O(4), one O(9), one F(1), and one F(2) atom. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(7), one O(8), one O(9), and one F(2) atom to form distorted VO5F octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a faceface with one V(3)O5F octahedra. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(4), one O(6), and two equivalent F(1) atoms. In the third V site, V(3) is bonded to one O(11), one O(2), one O(3), one O(5), one O(7), and one F(2) atom to form distorted VO5F octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a faceface with one V(1)O5F octahedra. There are two inequivalent P sites. In the first P site, 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 two equivalent V(1)O5F octahedra and corners with two equivalent V(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 33-57°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O5F octahedra and corners with two equivalent V(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 31-55°. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one K(2), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one K(2), one V(3), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one K(2), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one K(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one K(1), one V(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one K(1), one V(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to one K(1), one K(2), and one V(1) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one K(2), two equivalent K(1), and one V(2) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one K(1), one K(2), and one V(3) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one K(1) and one V(2) atom. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one K(2) 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), and two equivalent V(2) atoms. In the second F site, F(2) is bonded in a distorted trigonal pyramidal geometry to one K(1), one K(2), one V(1), and one V(3) atom.
K2V3P2O13F2 crystallizes in the triclinic P-1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to one O(11), one O(12), one O(5), one O(6), one O(8), one O(9), two equivalent O(10), one F(1), and one F(2) atom. The K(1)-O(11) bond length is 3.11 Å. The K(1)-O(12) bond length is 3.27 Å. The K(1)-O(5) bond length is 3.27 Å. The K(1)-O(6) bond length is 3.23 Å. The K(1)-O(8) bond length is 2.83 Å. The K(1)-O(9) bond length is 2.94 Å. There is one shorter (2.85 Å) and one longer (2.98 Å) K(1)-O(10) bond length. The K(1)-F(1) bond length is 2.80 Å. The K(1)-F(2) bond length is 2.81 Å. In the second K site, K(2) is bonded in a 9-coordinate geometry to one O(1), one O(10), one O(11), one O(13), one O(2), one O(4), one O(9), one F(1), and one F(2) atom. The K(2)-O(1) bond length is 3.10 Å. The K(2)-O(10) bond length is 2.76 Å. The K(2)-O(11) bond length is 3.14 Å. The K(2)-O(13) bond length is 2.87 Å. The K(2)-O(2) bond length is 2.98 Å. The K(2)-O(4) bond length is 3.23 Å. The K(2)-O(9) bond length is 2.99 Å. The K(2)-F(1) bond length is 3.23 Å. The K(2)-F(2) bond length is 2.77 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(7), one O(8), one O(9), and one F(2) atom to form distorted VO5F octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a faceface with one V(3)O5F octahedra. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(3) bond length is 2.14 Å. The V(1)-O(7) bond length is 2.12 Å. The V(1)-O(8) bond length is 1.97 Å. The V(1)-O(9) bond length is 1.64 Å. The V(1)-F(2) bond length is 2.11 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(4), one O(6), and two equivalent F(1) atoms. The V(2)-O(10) bond length is 1.67 Å. The V(2)-O(12) bond length is 1.66 Å. The V(2)-O(4) bond length is 1.97 Å. The V(2)-O(6) bond length is 2.20 Å. There is one shorter (1.97 Å) and one longer (2.29 Å) V(2)-F(1) bond length. In the third V site, V(3) is bonded to one O(11), one O(2), one O(3), one O(5), one O(7), and one F(2) atom to form distorted VO5F octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a faceface with one V(1)O5F octahedra. The V(3)-O(11) bond length is 1.61 Å. The V(3)-O(2) bond length is 1.86 Å. The V(3)-O(3) bond length is 2.09 Å. The V(3)-O(5) bond length is 1.85 Å. The V(3)-O(7) bond length is 2.05 Å. The V(3)-F(2) bond length is 2.11 Å. There are two inequivalent P sites. In the first P site, 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 two equivalent V(1)O5F octahedra and corners with two equivalent V(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 33-57°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.59 Å. The P(1)-O(4) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O5F octahedra and corners with two equivalent V(3)O5F octahedra. The corner-sharing octahedral tilt angles range from 31-55°. The P(2)-O(5) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.49 Å. The P(2)-O(7) bond length is 1.60 Å. The P(2)-O(8) bond length is 1.53 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one K(2), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one K(2), one V(3), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one K(2), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one K(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one K(1), one V(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one K(1), one V(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a single-bond geometry to one K(1), one K(2), and one V(1) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one K(2), two equivalent K(1), and one V(2) atom. In the eleventh O site, O(11) is bonded in a single-bond geometry to one K(1), one K(2), and one V(3) atom. In the twelfth O site, O(12) is bonded in a single-bond geometry to one K(1) and one V(2) atom. In the thirteenth O site, O(13) is bonded in a single-bond geometry to one K(2) 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), and two equivalent V(2) atoms. In the second F site, F(2) is bonded in a distorted trigonal pyramidal geometry to one K(1), one K(2), one V(1), and one V(3) atom.