K2VOF4 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. In the second K site, K(2) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. V(1) is bonded to one O(1), one F(1), one F(3), one F(4), and two equivalent F(2) atoms to form distorted corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles are 8°. O(1) is bonded in a distorted single-bond geometry to two equivalent K(1), two equivalent K(2), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one V(1) atom. In the second F site, F(2) is bonded in a 2-coordinate geometry to two equivalent K(1), two equivalent K(2), and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent K(1), two equivalent K(2), and one V(1) atom.
K2VOF4 crystallizes in the orthorhombic P2_12_12_1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. There is one shorter (2.86 Å) and one longer (3.06 Å) K(1)-O(1) bond length. There is one shorter (2.69 Å) and one longer (2.70 Å) K(1)-F(1) bond length. There is one shorter (2.96 Å) and one longer (3.02 Å) K(1)-F(2) bond length. There is one shorter (2.84 Å) and one longer (2.95 Å) K(1)-F(3) bond length. There is one shorter (2.86 Å) and one longer (3.01 Å) K(1)-F(4) bond length. In the second K site, K(2) is bonded in a 10-coordinate geometry to two equivalent O(1), two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. There is one shorter (2.84 Å) and one longer (2.98 Å) K(2)-O(1) bond length. There is one shorter (2.84 Å) and one longer (2.96 Å) K(2)-F(1) bond length. There is one shorter (3.03 Å) and one longer (3.10 Å) K(2)-F(2) bond length. There is one shorter (2.74 Å) and one longer (2.97 Å) K(2)-F(3) bond length. There is one shorter (2.78 Å) and one longer (3.04 Å) K(2)-F(4) bond length. V(1) is bonded to one O(1), one F(1), one F(3), one F(4), and two equivalent F(2) atoms to form distorted corner-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles are 8°. The V(1)-O(1) bond length is 1.66 Å. The V(1)-F(1) bond length is 1.97 Å. The V(1)-F(3) bond length is 1.93 Å. The V(1)-F(4) bond length is 1.93 Å. There is one shorter (2.01 Å) and one longer (2.28 Å) V(1)-F(2) bond length. O(1) is bonded in a distorted single-bond geometry to two equivalent K(1), two equivalent K(2), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one V(1) atom. In the second F site, F(2) is bonded in a 2-coordinate geometry to two equivalent K(1), two equivalent K(2), and two equivalent V(1) atoms. In the third F site, F(3) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one V(1) atom. In the fourth F site, F(4) is bonded in a distorted single-bond geometry to two equivalent K(1), two equivalent K(2), and one V(1) atom.