K2VO2F3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to four equivalent O(1), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. In the second K site, K(2) is bonded in a 10-coordinate geometry to four equivalent O(1), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. V(1) is bonded to two equivalent O(1), one F(1), one F(3), and two equivalent F(2) atoms to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedra are not tilted. 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 three inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent K(1), two equivalent K(2), and one V(1) atom. In the second F site, F(2) is bonded to two equivalent K(1), two equivalent K(2), and two equivalent V(1) atoms to form distorted face-sharing FK4V2 octahedra. 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.
K2VO2F3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 10-coordinate geometry to four equivalent O(1), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. There are two shorter (2.97 Å) and two longer (2.98 Å) K(1)-O(1) bond lengths. Both K(1)-F(1) bond lengths are 2.90 Å. Both K(1)-F(2) bond lengths are 2.90 Å. There is one shorter (2.65 Å) and one longer (2.71 Å) K(1)-F(3) bond length. In the second K site, K(2) is bonded in a 10-coordinate geometry to four equivalent O(1), two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. There are two shorter (2.79 Å) and two longer (3.05 Å) K(2)-O(1) bond lengths. There is one shorter (2.77 Å) and one longer (2.90 Å) K(2)-F(1) bond length. Both K(2)-F(2) bond lengths are 2.95 Å. Both K(2)-F(3) bond lengths are 2.91 Å. V(1) is bonded to two equivalent O(1), one F(1), one F(3), and two equivalent F(2) atoms to form distorted corner-sharing VO2F4 octahedra. The corner-sharing octahedra are not tilted. Both V(1)-O(1) bond lengths are 1.67 Å. The V(1)-F(1) bond length is 1.89 Å. The V(1)-F(3) bond length is 1.93 Å. Both V(1)-F(2) bond lengths are 2.24 Å. 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 three inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to two equivalent K(1), two equivalent K(2), and one V(1) atom. In the second F site, F(2) is bonded to two equivalent K(1), two equivalent K(2), and two equivalent V(1) atoms to form distorted face-sharing FK4V2 octahedra. 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.