VZnSF5 crystallizes in the triclinic P1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(10), one F(2), one F(4), one F(5), one F(7), and one F(9) atom to form VF6 octahedra that share corners with two equivalent V(2)F6 octahedra, corners with two equivalent Zn(1)SF3 tetrahedra, and corners with two equivalent Zn(2)SF3 tetrahedra. The corner-sharing octahedral tilt angles are 30°. In the second V site, V(2) is bonded to one F(1), one F(10), one F(3), one F(6), one F(8), and one F(9) atom to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra,  a cornercorner with one Zn(1)SF3 tetrahedra, and  a cornercorner with one Zn(2)SF3 tetrahedra. The corner-sharing octahedral tilt angles are 30°. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1), one F(3), one F(4), and one F(7) atom to form distorted ZnSF3 tetrahedra that share  a cornercorner with one V(2)F6 octahedra and corners with two equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-58°. In the second Zn site, Zn(2) is bonded to one S(2), one F(1), one F(2), and one F(5) atom to form distorted ZnSF3 tetrahedra that share  a cornercorner with one V(2)F6 octahedra and corners with two equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-58°. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted water-like geometry to one Zn(1) and one S(2) atom. In the second S site, S(2) is bonded in a distorted water-like geometry to one Zn(2) and one S(1) atom. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(2) and one Zn(2) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one Zn(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(2) and one Zn(1) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one Zn(1) atom. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one V(1) and one Zn(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 120 degrees geometry to one V(1) and one Zn(1) atom. In the eighth F site, F(8) is bonded in a single-bond geometry to one V(2) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom.
VZnSF5 crystallizes in the triclinic P1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one F(10), one F(2), one F(4), one F(5), one F(7), and one F(9) atom to form VF6 octahedra that share corners with two equivalent V(2)F6 octahedra, corners with two equivalent Zn(1)SF3 tetrahedra, and corners with two equivalent Zn(2)SF3 tetrahedra. The corner-sharing octahedral tilt angles are 30°. The V(1)-F(10) bond length is 2.00 Å. The V(1)-F(2) bond length is 1.94 Å. The V(1)-F(4) bond length is 1.94 Å. The V(1)-F(5) bond length is 1.99 Å. The V(1)-F(7) bond length is 1.98 Å. The V(1)-F(9) bond length is 2.00 Å. In the second V site, V(2) is bonded to one F(1), one F(10), one F(3), one F(6), one F(8), and one F(9) atom to form VF6 octahedra that share corners with two equivalent V(1)F6 octahedra,  a cornercorner with one Zn(1)SF3 tetrahedra, and  a cornercorner with one Zn(2)SF3 tetrahedra. The corner-sharing octahedral tilt angles are 30°. The V(2)-F(1) bond length is 1.95 Å. The V(2)-F(10) bond length is 1.94 Å. The V(2)-F(3) bond length is 1.95 Å. The V(2)-F(6) bond length is 1.79 Å. The V(2)-F(8) bond length is 1.80 Å. The V(2)-F(9) bond length is 1.94 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(1), one F(3), one F(4), and one F(7) atom to form distorted ZnSF3 tetrahedra that share  a cornercorner with one V(2)F6 octahedra and corners with two equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-58°. The Zn(1)-S(1) bond length is 2.29 Å. The Zn(1)-F(3) bond length is 1.98 Å. The Zn(1)-F(4) bond length is 1.99 Å. The Zn(1)-F(7) bond length is 1.96 Å. In the second Zn site, Zn(2) is bonded to one S(2), one F(1), one F(2), and one F(5) atom to form distorted ZnSF3 tetrahedra that share  a cornercorner with one V(2)F6 octahedra and corners with two equivalent V(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 38-58°. The Zn(2)-S(2) bond length is 2.29 Å. The Zn(2)-F(1) bond length is 1.98 Å. The Zn(2)-F(2) bond length is 1.99 Å. The Zn(2)-F(5) bond length is 1.96 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted water-like geometry to one Zn(1) and one S(2) atom. The S(1)-S(2) bond length is 2.00 Å. In the second S site, S(2) is bonded in a distorted water-like geometry to one Zn(2) and one S(1) atom. There are ten inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one V(2) and one Zn(2) atom. In the second F site, F(2) is bonded in a bent 150 degrees geometry to one V(1) and one Zn(2) atom. In the third F site, F(3) is bonded in a bent 150 degrees geometry to one V(2) and one Zn(1) atom. In the fourth F site, F(4) is bonded in a bent 150 degrees geometry to one V(1) and one Zn(1) atom. In the fifth F site, F(5) is bonded in a bent 120 degrees geometry to one V(1) and one Zn(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 120 degrees geometry to one V(1) and one Zn(1) atom. In the eighth F site, F(8) is bonded in a single-bond geometry to one V(2) atom. In the ninth F site, F(9) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the tenth F site, F(10) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom.