V3ZnO8 crystallizes in the orthorhombic Iba2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra and corners with three equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-69°. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one Zn(1)O6 octahedra, corners with three equivalent V(1)O4 tetrahedra, and edges with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 39°. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), and two equivalent O(7) atoms. Zn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form distorted ZnO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with three equivalent V(1)O4 tetrahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 39°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Zn(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one Zn(1) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(3) and one Zn(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(2) and one V(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom.
V3ZnO8 crystallizes in the orthorhombic Iba2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(6), one O(7), and one O(8) atom to form VO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra and corners with three equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-69°. The V(1)-O(2) bond length is 1.72 Å. The V(1)-O(6) bond length is 1.73 Å. The V(1)-O(7) bond length is 1.82 Å. The V(1)-O(8) bond length is 1.73 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one Zn(1)O6 octahedra, corners with three equivalent V(1)O4 tetrahedra, and edges with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 39°. The V(2)-O(1) bond length is 1.98 Å. The V(2)-O(2) bond length is 2.08 Å. The V(2)-O(3) bond length is 1.68 Å. The V(2)-O(5) bond length is 2.00 Å. The V(2)-O(6) bond length is 2.16 Å. The V(2)-O(8) bond length is 2.07 Å. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), and two equivalent O(7) atoms. The V(3)-O(1) bond length is 1.86 Å. The V(3)-O(4) bond length is 1.66 Å. The V(3)-O(5) bond length is 1.70 Å. There is one shorter (2.03 Å) and one longer (2.10 Å) V(3)-O(7) bond length. Zn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(8) atom to form distorted ZnO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with three equivalent V(1)O4 tetrahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 39°. The Zn(1)-O(1) bond length is 2.09 Å. The Zn(1)-O(2) bond length is 2.28 Å. The Zn(1)-O(3) bond length is 2.00 Å. The Zn(1)-O(4) bond length is 2.05 Å. The Zn(1)-O(6) bond length is 2.13 Å. The Zn(1)-O(8) bond length is 2.20 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Zn(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one Zn(1) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(3) and one Zn(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one V(2) and one V(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one Zn(1) atom.