KVF4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one F(3), two equivalent F(5), and four equivalent F(4) atoms. In the second K site, K(2) is bonded in a 9-coordinate geometry to one F(2), two equivalent F(1), two equivalent F(4), and four equivalent F(5) atoms. V(1) is bonded to one F(2), one F(3), one F(4), one F(5), and two equivalent F(1) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 25-35°. There are five inequivalent F sites. In the first F site, F(4) is bonded to one K(2), two equivalent K(1), and one V(1) atom to form a mixture of distorted corner and edge-sharing FK3V tetrahedra. In the second F site, F(5) is bonded to one K(1), two equivalent K(2), and one V(1) atom to form a mixture of distorted corner and edge-sharing FK3V tetrahedra. In the third F site, F(1) is bonded in a 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 distorted bent 150 degrees geometry to one K(2) and two equivalent V(1) atoms. In the fifth F site, F(3) is bonded in a distorted bent 150 degrees geometry to one K(1) and two equivalent V(1) atoms.
KVF4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 7-coordinate geometry to one F(3), two equivalent F(5), and four equivalent F(4) atoms. The K(1)-F(3) bond length is 2.83 Å. Both K(1)-F(5) bond lengths are 2.63 Å. There are two shorter (2.62 Å) and two longer (2.65 Å) K(1)-F(4) bond lengths. In the second K site, K(2) is bonded in a 9-coordinate geometry to one F(2), two equivalent F(1), two equivalent F(4), and four equivalent F(5) atoms. The K(2)-F(2) bond length is 2.94 Å. Both K(2)-F(1) bond lengths are 3.08 Å. Both K(2)-F(4) bond lengths are 2.67 Å. There are two shorter (2.66 Å) and two longer (2.70 Å) K(2)-F(5) bond lengths. V(1) is bonded to one F(2), one F(3), one F(4), one F(5), and two equivalent F(1) atoms to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 25-35°. The V(1)-F(2) bond length is 1.98 Å. The V(1)-F(3) bond length is 1.99 Å. The V(1)-F(4) bond length is 1.89 Å. The V(1)-F(5) bond length is 1.89 Å. Both V(1)-F(1) bond lengths are 1.97 Å. There are five inequivalent F sites. In the first F site, F(4) is bonded to one K(2), two equivalent K(1), and one V(1) atom to form a mixture of distorted corner and edge-sharing FK3V tetrahedra. In the second F site, F(5) is bonded to one K(1), two equivalent K(2), and one V(1) atom to form a mixture of distorted corner and edge-sharing FK3V tetrahedra. In the third F site, F(1) is bonded in a 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 distorted bent 150 degrees geometry to one K(2) and two equivalent V(1) atoms. In the fifth F site, F(3) is bonded in a distorted bent 150 degrees geometry to one K(1) and two equivalent V(1) atoms.