ZnV2O4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-62°. In the second V site, V(2) is bonded to one O(1), two equivalent O(3), and three equivalent O(2) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-62°. Zn(1) is bonded in a 7-coordinate geometry to one O(3), two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one V(2), two equivalent V(1), and two equivalent Zn(1) atoms. In the second O site, O(2) is bonded to three equivalent V(2) and two equivalent Zn(1) atoms to form OV3Zn2 trigonal bipyramids that share corners with two equivalent O(4)V3Zn2 trigonal bipyramids, corners with six equivalent O(3)V3Zn trigonal pyramids,  an edgeedge with one O(4)V3Zn2 trigonal bipyramid, edges with four equivalent O(2)V3Zn2 trigonal bipyramids, and  an edgeedge with one O(3)V3Zn trigonal pyramid. In the third O site, O(3) is bonded to one V(1), two equivalent V(2), and one Zn(1) atom to form distorted OV3Zn trigonal pyramids that share  a cornercorner with one O(4)V3Zn2 trigonal bipyramid, corners with six equivalent O(2)V3Zn2 trigonal bipyramids, corners with two equivalent O(3)V3Zn trigonal pyramids,  an edgeedge with one O(2)V3Zn2 trigonal bipyramid, and edges with two equivalent O(4)V3Zn2 trigonal bipyramids. In the fourth O site, O(4) is bonded to three equivalent V(1) and two equivalent Zn(1) atoms to form distorted OV3Zn2 trigonal bipyramids that share corners with two equivalent O(2)V3Zn2 trigonal bipyramids,  a cornercorner with one O(3)V3Zn trigonal pyramid,  an edgeedge with one O(2)V3Zn2 trigonal bipyramid, edges with four equivalent O(4)V3Zn2 trigonal bipyramids, and edges with two equivalent O(3)V3Zn trigonal pyramids.
ZnV2O4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-62°. The V(1)-O(3) bond length is 1.97 Å. Both V(1)-O(1) bond lengths are 2.05 Å. There is one shorter (2.02 Å) and two longer (2.12 Å) V(1)-O(4) bond lengths. In the second V site, V(2) is bonded to one O(1), two equivalent O(3), and three equivalent O(2) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 50-62°. The V(2)-O(1) bond length is 2.06 Å. Both V(2)-O(3) bond lengths are 1.97 Å. There is one shorter (2.10 Å) and two longer (2.11 Å) V(2)-O(2) bond lengths. Zn(1) is bonded in a 7-coordinate geometry to one O(3), two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms. The Zn(1)-O(3) bond length is 2.36 Å. Both Zn(1)-O(1) bond lengths are 2.43 Å. Both Zn(1)-O(2) bond lengths are 2.23 Å. Both Zn(1)-O(4) bond lengths are 2.23 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one V(2), two equivalent V(1), and two equivalent Zn(1) atoms. In the second O site, O(2) is bonded to three equivalent V(2) and two equivalent Zn(1) atoms to form OV3Zn2 trigonal bipyramids that share corners with two equivalent O(4)V3Zn2 trigonal bipyramids, corners with six equivalent O(3)V3Zn trigonal pyramids,  an edgeedge with one O(4)V3Zn2 trigonal bipyramid, edges with four equivalent O(2)V3Zn2 trigonal bipyramids, and  an edgeedge with one O(3)V3Zn trigonal pyramid. In the third O site, O(3) is bonded to one V(1), two equivalent V(2), and one Zn(1) atom to form distorted OV3Zn trigonal pyramids that share  a cornercorner with one O(4)V3Zn2 trigonal bipyramid, corners with six equivalent O(2)V3Zn2 trigonal bipyramids, corners with two equivalent O(3)V3Zn trigonal pyramids,  an edgeedge with one O(2)V3Zn2 trigonal bipyramid, and edges with two equivalent O(4)V3Zn2 trigonal bipyramids. In the fourth O site, O(4) is bonded to three equivalent V(1) and two equivalent Zn(1) atoms to form distorted OV3Zn2 trigonal bipyramids that share corners with two equivalent O(2)V3Zn2 trigonal bipyramids,  a cornercorner with one O(3)V3Zn trigonal pyramid,  an edgeedge with one O(2)V3Zn2 trigonal bipyramid, edges with four equivalent O(4)V3Zn2 trigonal bipyramids, and edges with two equivalent O(3)V3Zn trigonal pyramids.