VF4 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(7) atom to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 32-43°. In the second V site, V(2) is bonded to one F(2), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 32-43°. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a single-bond geometry to one V(1) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one V(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the eighth F site, F(8) is bonded in a single-bond geometry to one V(2) atom.
VF4 crystallizes in the orthorhombic Pna2_1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(1), one F(2), one F(3), one F(4), one F(5), and one F(7) atom to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 32-43°. The V(1)-F(1) bond length is 1.75 Å. The V(1)-F(2) bond length is 1.95 Å. The V(1)-F(3) bond length is 1.74 Å. The V(1)-F(4) bond length is 2.04 Å. The V(1)-F(5) bond length is 1.99 Å. The V(1)-F(7) bond length is 2.05 Å. In the second V site, V(2) is bonded to one F(2), one F(4), one F(5), one F(6), one F(7), and one F(8) atom to form corner-sharing VF6 octahedra. The corner-sharing octahedral tilt angles range from 32-43°. The V(2)-F(2) bond length is 2.03 Å. The V(2)-F(4) bond length is 1.93 Å. The V(2)-F(5) bond length is 2.04 Å. The V(2)-F(6) bond length is 1.76 Å. The V(2)-F(7) bond length is 1.95 Å. The V(2)-F(8) bond length is 1.76 Å. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a single-bond geometry to one V(1) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the third F site, F(3) is bonded in a single-bond geometry to one V(1) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth F site, F(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth F site, F(6) is bonded in a single-bond geometry to one V(2) atom. In the seventh F site, F(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the eighth F site, F(8) is bonded in a single-bond geometry to one V(2) atom.