KVOF3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to two equivalent O(1), one F(2), two equivalent F(4), and four equivalent F(3) atoms. In the second K site, K(2) is bonded in a 8-coordinate geometry to two equivalent O(1), one F(1), one 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(2), one F(3), and two equivalent F(4) atoms to form a mixture of distorted corner and edge-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 27-43°. O(1) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(3) is bonded in a distorted single-bond geometry to one K(2), two equivalent K(1), and one V(1) atom. In the second F site, F(4) is bonded to one K(1), one K(2), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing FK2V2 tetrahedra. In the third F site, F(1) is bonded in a distorted bent 150 degrees geometry to one K(2) and two equivalent V(1) atoms. In the fourth F site, F(2) is bonded in a 4-coordinate geometry to one K(1), one K(2), and two equivalent V(1) atoms.
KVOF3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 9-coordinate geometry to two equivalent O(1), one F(2), two equivalent F(4), and four equivalent F(3) atoms. Both K(1)-O(1) bond lengths are 2.84 Å. The K(1)-F(2) bond length is 2.94 Å. Both K(1)-F(4) bond lengths are 2.74 Å. There are two shorter (2.79 Å) and two longer (2.93 Å) K(1)-F(3) bond lengths. In the second K site, K(2) is bonded in a 8-coordinate geometry to two equivalent O(1), one F(1), one F(2), two equivalent F(3), and two equivalent F(4) atoms. Both K(2)-O(1) bond lengths are 2.89 Å. The K(2)-F(1) bond length is 2.97 Å. The K(2)-F(2) bond length is 2.90 Å. Both K(2)-F(3) bond lengths are 2.74 Å. Both K(2)-F(4) bond lengths are 2.89 Å. V(1) is bonded to one O(1), one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form a mixture of distorted corner and edge-sharing VOF5 octahedra. The corner-sharing octahedral tilt angles range from 27-43°. The V(1)-O(1) bond length is 1.64 Å. The V(1)-F(1) bond length is 2.01 Å. The V(1)-F(2) bond length is 2.03 Å. The V(1)-F(3) bond length is 1.90 Å. There is one shorter (2.01 Å) and one longer (2.21 Å) V(1)-F(4) bond length. O(1) is bonded in a distorted single-bond geometry to one K(1), one K(2), and one V(1) atom. There are four inequivalent F sites. In the first F site, F(3) is bonded in a distorted single-bond geometry to one K(2), two equivalent K(1), and one V(1) atom. In the second F site, F(4) is bonded to one K(1), one K(2), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing FK2V2 tetrahedra. In the third F site, F(1) is bonded in a distorted bent 150 degrees geometry to one K(2) and two equivalent V(1) atoms. In the fourth F site, F(2) is bonded in a 4-coordinate geometry to one K(1), one K(2), and two equivalent V(1) atoms.