Zn3(VO4)2 crystallizes in the orthorhombic Cmce space group. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with three equivalent Zn(2)O6 octahedra and corners with six equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZnO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra, edges with two equivalent Zn(1)O6 octahedra, and edges with two equivalent Zn(2)O6 octahedra. In the second Zn site, Zn(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form ZnO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra and edges with four equivalent Zn(1)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one Zn(1), and one Zn(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one V(1), one Zn(2), and two equivalent Zn(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Zn(1) atoms.
Zn3(VO4)2 crystallizes in the orthorhombic Cmce space group. V(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form VO4 tetrahedra that share corners with three equivalent Zn(2)O6 octahedra and corners with six equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-57°. The V(1)-O(2) bond length is 1.82 Å. The V(1)-O(3) bond length is 1.76 Å. Both V(1)-O(1) bond lengths are 1.73 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZnO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra, edges with two equivalent Zn(1)O6 octahedra, and edges with two equivalent Zn(2)O6 octahedra. Both Zn(1)-O(1) bond lengths are 2.11 Å. Both Zn(1)-O(2) bond lengths are 2.23 Å. Both Zn(1)-O(3) bond lengths are 2.05 Å. In the second Zn site, Zn(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form ZnO6 octahedra that share corners with six equivalent V(1)O4 tetrahedra and edges with four equivalent Zn(1)O6 octahedra. Both Zn(2)-O(2) bond lengths are 2.05 Å. All Zn(2)-O(1) bond lengths are 2.18 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one V(1), one Zn(1), and one Zn(2) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one V(1), one Zn(2), and two equivalent Zn(1) atoms. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent Zn(1) atoms.