VZnF4 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with four equivalent V(2)F6 octahedra and corners with six equivalent Zn(1)F5 square pyramids. The corner-sharing octahedral tilt angles range from 55-57°. In the second V site, V(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form VF6 octahedra that share corners with four equivalent V(1)F6 octahedra, corners with four equivalent Zn(1)F5 square pyramids, and edges with two equivalent Zn(1)F5 square pyramids. The corner-sharing octahedral tilt angles range from 55-57°. Zn(1) is bonded to one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form ZnF5 square pyramids that share corners with two equivalent V(2)F6 octahedra, corners with three equivalent V(1)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and  an edgeedge with one Zn(1)F5 square pyramid. The corner-sharing octahedral tilt angles range from 47-59°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one V(1) and one Zn(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one V(2) and two equivalent Zn(1) atoms.
VZnF4 crystallizes in the triclinic P-1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form VF6 octahedra that share corners with four equivalent V(2)F6 octahedra and corners with six equivalent Zn(1)F5 square pyramids. The corner-sharing octahedral tilt angles range from 55-57°. Both V(1)-F(1) bond lengths are 2.08 Å. Both V(1)-F(2) bond lengths are 2.22 Å. Both V(1)-F(3) bond lengths are 2.18 Å. In the second V site, V(2) is bonded to two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms to form VF6 octahedra that share corners with four equivalent V(1)F6 octahedra, corners with four equivalent Zn(1)F5 square pyramids, and edges with two equivalent Zn(1)F5 square pyramids. The corner-sharing octahedral tilt angles range from 55-57°. Both V(2)-F(2) bond lengths are 2.17 Å. Both V(2)-F(3) bond lengths are 2.15 Å. Both V(2)-F(4) bond lengths are 2.08 Å. Zn(1) is bonded to one F(1), one F(2), one F(3), and two equivalent F(4) atoms to form ZnF5 square pyramids that share corners with two equivalent V(2)F6 octahedra, corners with three equivalent V(1)F6 octahedra,  an edgeedge with one V(2)F6 octahedra, and  an edgeedge with one Zn(1)F5 square pyramid. The corner-sharing octahedral tilt angles range from 47-59°. The Zn(1)-F(1) bond length is 1.91 Å. The Zn(1)-F(2) bond length is 2.08 Å. The Zn(1)-F(3) bond length is 2.01 Å. There is one shorter (2.08 Å) and one longer (2.11 Å) Zn(1)-F(4) bond length. There are four inequivalent F sites. In the first F site, F(1) is bonded in a bent 120 degrees geometry to one V(1) and one Zn(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one V(2) and two equivalent Zn(1) atoms.