V4ZnO8 crystallizes in the monoclinic Cm space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(7), two equivalent O(4), and two equivalent O(5) atoms to form distorted VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent Zn(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 48-50°. In the second V site, V(2) is bonded to one O(4), one O(8), two equivalent O(3), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent Zn(1)O5 square pyramids, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  a faceface with one Zn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 48-54°. In the third V site, V(3) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent Zn(1)O5 square pyramids, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. In the fourth V site, V(4) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent Zn(1)O5 square pyramids, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and  an edgeedge with one Zn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 51-54°. Zn(1) is bonded to one O(4), two equivalent O(6), and two equivalent O(7) atoms to form ZnO5 square pyramids that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Zn(1)O5 square pyramids, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-55°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(3) and two equivalent V(4) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(4) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded to one V(2), two equivalent V(1), and one Zn(1) atom to form OV3Zn trigonal pyramids that share corners with two equivalent O(4)V3Zn trigonal pyramids, edges with two equivalent O(7)V3Zn2 square pyramids, and edges with two equivalent O(6)V3Zn2 trigonal bipyramids. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one V(4) and two equivalent V(1) atoms. In the sixth O site, O(6) is bonded to one V(3), two equivalent V(2), and two equivalent Zn(1) atoms to form distorted OV3Zn2 trigonal bipyramids that share corners with two equivalent O(7)V3Zn2 square pyramids,  an edgeedge with one O(7)V3Zn2 square pyramid, edges with two equivalent O(6)V3Zn2 trigonal bipyramids, and edges with two equivalent O(4)V3Zn trigonal pyramids. In the seventh O site, O(7) is bonded to one V(1), two equivalent V(4), and two equivalent Zn(1) atoms to form OV3Zn2 square pyramids that share corners with two equivalent O(6)V3Zn2 trigonal bipyramids, edges with two equivalent O(7)V3Zn2 square pyramids,  an edgeedge with one O(6)V3Zn2 trigonal bipyramid, and edges with two equivalent O(4)V3Zn trigonal pyramids. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one V(2) and two equivalent V(3) atoms.
V4ZnO8 crystallizes in the monoclinic Cm space group. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(7), two equivalent O(4), and two equivalent O(5) atoms to form distorted VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent Zn(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 48-50°. The V(1)-O(2) bond length is 1.80 Å. The V(1)-O(7) bond length is 2.28 Å. Both V(1)-O(4) bond lengths are 2.04 Å. Both V(1)-O(5) bond lengths are 1.94 Å. In the second V site, V(2) is bonded to one O(4), one O(8), two equivalent O(3), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent Zn(1)O5 square pyramids, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and  a faceface with one Zn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 48-54°. The V(2)-O(4) bond length is 1.98 Å. The V(2)-O(8) bond length is 1.80 Å. Both V(2)-O(3) bond lengths are 1.92 Å. Both V(2)-O(6) bond lengths are 2.21 Å. In the third V site, V(3) is bonded to one O(1), one O(6), two equivalent O(2), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent Zn(1)O5 square pyramids, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The V(3)-O(1) bond length is 1.91 Å. The V(3)-O(6) bond length is 2.10 Å. Both V(3)-O(2) bond lengths are 2.06 Å. Both V(3)-O(8) bond lengths are 2.04 Å. In the fourth V site, V(4) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent Zn(1)O5 square pyramids, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and  an edgeedge with one Zn(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 51-54°. The V(4)-O(3) bond length is 2.04 Å. The V(4)-O(5) bond length is 2.02 Å. Both V(4)-O(1) bond lengths are 1.97 Å. Both V(4)-O(7) bond lengths are 2.19 Å. Zn(1) is bonded to one O(4), two equivalent O(6), and two equivalent O(7) atoms to form ZnO5 square pyramids that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Zn(1)O5 square pyramids, and  a faceface with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-55°. The Zn(1)-O(4) bond length is 2.15 Å. Both Zn(1)-O(6) bond lengths are 2.13 Å. Both Zn(1)-O(7) bond lengths are 2.05 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one V(3) and two equivalent V(4) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one V(1) and two equivalent V(3) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(4) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded to one V(2), two equivalent V(1), and one Zn(1) atom to form OV3Zn trigonal pyramids that share corners with two equivalent O(4)V3Zn trigonal pyramids, edges with two equivalent O(7)V3Zn2 square pyramids, and edges with two equivalent O(6)V3Zn2 trigonal bipyramids. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one V(4) and two equivalent V(1) atoms. In the sixth O site, O(6) is bonded to one V(3), two equivalent V(2), and two equivalent Zn(1) atoms to form distorted OV3Zn2 trigonal bipyramids that share corners with two equivalent O(7)V3Zn2 square pyramids,  an edgeedge with one O(7)V3Zn2 square pyramid, edges with two equivalent O(6)V3Zn2 trigonal bipyramids, and edges with two equivalent O(4)V3Zn trigonal pyramids. In the seventh O site, O(7) is bonded to one V(1), two equivalent V(4), and two equivalent Zn(1) atoms to form OV3Zn2 square pyramids that share corners with two equivalent O(6)V3Zn2 trigonal bipyramids, edges with two equivalent O(7)V3Zn2 square pyramids,  an edgeedge with one O(6)V3Zn2 trigonal bipyramid, and edges with two equivalent O(4)V3Zn trigonal pyramids. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to one V(2) and two equivalent V(3) atoms.