ZnV2O4 crystallizes in the orthorhombic Imma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share edges with two equivalent V(1)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Zn(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Zn(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. Zn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form ZnO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Zn(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(2), two equivalent V(1), and one Zn(1) atom. In the second O site, O(2) is bonded to one V(1), two equivalent V(2), and two equivalent Zn(1) atoms to form a mixture of corner and edge-sharing OV3Zn2 square pyramids.
ZnV2O4 crystallizes in the orthorhombic Imma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form VO6 octahedra that share edges with two equivalent V(1)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and edges with four equivalent Zn(1)O6 octahedra. Both V(1)-O(2) bond lengths are 2.05 Å. All V(1)-O(1) bond lengths are 2.02 Å. In the second V site, V(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Zn(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Zn(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. Both V(2)-O(1) bond lengths are 2.07 Å. All V(2)-O(2) bond lengths are 2.14 Å. Zn(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form ZnO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Zn(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. Both Zn(1)-O(1) bond lengths are 2.13 Å. All Zn(1)-O(2) bond lengths are 2.19 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(2), two equivalent V(1), and one Zn(1) atom. In the second O site, O(2) is bonded to one V(1), two equivalent V(2), and two equivalent Zn(1) atoms to form a mixture of corner and edge-sharing OV3Zn2 square pyramids.