ZnV2O4 crystallizes in the orthorhombic Cmcm space group. V(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-57°. Zn(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent V(1) and two equivalent Zn(1) atoms to form distorted OV3Zn2 trigonal bipyramids that share corners with five equivalent O(2)V2Zn2 tetrahedra, corners with two equivalent O(1)V3Zn2 trigonal bipyramids,  an edgeedge with one O(2)V2Zn2 tetrahedra, and edges with five equivalent O(1)V3Zn2 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent V(1) and two equivalent Zn(1) atoms to form OV2Zn2 tetrahedra that share corners with two equivalent O(2)V2Zn2 tetrahedra, corners with ten equivalent O(1)V3Zn2 trigonal bipyramids, and edges with two equivalent O(1)V3Zn2 trigonal bipyramids. In the third O site, O(3) is bonded in a square co-planar geometry to four equivalent V(1) atoms.
ZnV2O4 crystallizes in the orthorhombic Cmcm space group. V(1) is bonded to one O(2), two equivalent O(3), and three equivalent O(1) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-57°. The V(1)-O(2) bond length is 2.04 Å. Both V(1)-O(3) bond lengths are 2.09 Å. There are two shorter (2.04 Å) and one longer (2.10 Å) V(1)-O(1) bond length. Zn(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Zn(1)-O(2) bond lengths are 2.04 Å. All Zn(1)-O(1) bond lengths are 2.33 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent V(1) and two equivalent Zn(1) atoms to form distorted OV3Zn2 trigonal bipyramids that share corners with five equivalent O(2)V2Zn2 tetrahedra, corners with two equivalent O(1)V3Zn2 trigonal bipyramids,  an edgeedge with one O(2)V2Zn2 tetrahedra, and edges with five equivalent O(1)V3Zn2 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent V(1) and two equivalent Zn(1) atoms to form OV2Zn2 tetrahedra that share corners with two equivalent O(2)V2Zn2 tetrahedra, corners with ten equivalent O(1)V3Zn2 trigonal bipyramids, and edges with two equivalent O(1)V3Zn2 trigonal bipyramids. In the third O site, O(3) is bonded in a square co-planar geometry to four equivalent V(1) atoms.