ZnV2O4 is Spinel-like structured and crystallizes in the trigonal P3m1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one V(6)O4 tetrahedra,  a cornercorner with one Zn(2)O4 tetrahedra, corners with two equivalent Zn(1)O4 tetrahedra, corners with two equivalent Zn(5)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one Zn(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. In the second V site, V(2) is bonded to one O(6), one O(9), two equivalent O(4), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one Zn(4)O4 tetrahedra,  a cornercorner with one Zn(5)O4 tetrahedra, corners with two equivalent Zn(2)O4 tetrahedra, corners with two equivalent Zn(6)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. In the third V site, V(3) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Zn(2)O4 tetrahedra, corners with three equivalent Zn(5)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. In the fourth V site, V(4) is bonded to one O(10), one O(12), two equivalent O(11), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one Zn(6)O4 tetrahedra, corners with two equivalent V(6)O4 tetrahedra, corners with two equivalent Zn(4)O4 tetrahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one Zn(3)O6 octahedra, and edges with four equivalent V(4)O6 octahedra. In the fifth V site, V(5) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent Zn(4)O4 tetrahedra, corners with three equivalent Zn(6)O4 tetrahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. In the sixth V site, V(6) is bonded to one O(5) and three equivalent O(11) atoms to form VO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent Zn(3)O6 octahedra, and corners with six equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-61°. There are six inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(10) and three equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with three equivalent V(4)O6 octahedra, corners with three equivalent Zn(3)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-59°. In the second Zn site, Zn(2) is bonded to one O(2) and three equivalent O(4) atoms to form ZnO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. In the third Zn site, Zn(3) is bonded to three equivalent O(1) and three equivalent O(11) atoms to form ZnO6 octahedra that share corners with three equivalent V(6)O4 tetrahedra, corners with three equivalent Zn(1)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. In the fourth Zn site, Zn(4) is bonded to one O(6) and three equivalent O(8) atoms to form ZnO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and corners with six equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. In the fifth Zn site, Zn(5) is bonded to one O(9) and three equivalent O(3) atoms to form ZnO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. In the sixth Zn site, Zn(6) is bonded to one O(12) and three equivalent O(7) atoms to form ZnO4 tetrahedra that share corners with three equivalent V(4)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent V(1), one Zn(1), and one Zn(3) atom. In the second O site, O(2) is bonded to three equivalent V(1) and one Zn(2) atom to form distorted corner-sharing OV3Zn trigonal pyramids. In the third O site, O(3) is bonded to one V(3), two equivalent V(1), and one Zn(5) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the fourth O site, O(4) is bonded to one V(3), two equivalent V(2), and one Zn(2) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one V(6) and three equivalent V(1) atoms. In the sixth O site, O(6) is bonded to three equivalent V(2) and one Zn(4) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the seventh O site, O(7) is bonded to one V(5), two equivalent V(2), and one Zn(6) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the eighth O site, O(8) is bonded to one V(5), two equivalent V(4), and one Zn(4) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the ninth O site, O(9) is bonded to three equivalent V(2) and one Zn(5) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the tenth O site, O(10) is bonded to three equivalent V(4) and one Zn(1) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one V(6), two equivalent V(4), and one Zn(3) atom. In the twelfth O site, O(12) is bonded to three equivalent V(4) and one Zn(6) atom to form distorted corner-sharing OV3Zn trigonal pyramids.
ZnV2O4 is Spinel-like structured and crystallizes in the trigonal P3m1 space group. There are six inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one V(6)O4 tetrahedra,  a cornercorner with one Zn(2)O4 tetrahedra, corners with two equivalent Zn(1)O4 tetrahedra, corners with two equivalent Zn(5)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one Zn(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The V(1)-O(2) bond length is 2.06 Å. The V(1)-O(5) bond length is 2.11 Å. Both V(1)-O(1) bond lengths are 2.03 Å. Both V(1)-O(3) bond lengths are 2.06 Å. In the second V site, V(2) is bonded to one O(6), one O(9), two equivalent O(4), and two equivalent O(7) atoms to form VO6 octahedra that share  a cornercorner with one Zn(4)O4 tetrahedra,  a cornercorner with one Zn(5)O4 tetrahedra, corners with two equivalent Zn(2)O4 tetrahedra, corners with two equivalent Zn(6)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The V(2)-O(6) bond length is 2.06 Å. The V(2)-O(9) bond length is 2.05 Å. Both V(2)-O(4) bond lengths are 2.06 Å. Both V(2)-O(7) bond lengths are 2.07 Å. In the third V site, V(3) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form VO6 octahedra that share corners with three equivalent Zn(2)O4 tetrahedra, corners with three equivalent Zn(5)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. All V(3)-O(3) bond lengths are 2.06 Å. All V(3)-O(4) bond lengths are 2.05 Å. In the fourth V site, V(4) is bonded to one O(10), one O(12), two equivalent O(11), and two equivalent O(8) atoms to form VO6 octahedra that share  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one Zn(6)O4 tetrahedra, corners with two equivalent V(6)O4 tetrahedra, corners with two equivalent Zn(4)O4 tetrahedra,  an edgeedge with one V(5)O6 octahedra,  an edgeedge with one Zn(3)O6 octahedra, and edges with four equivalent V(4)O6 octahedra. The V(4)-O(10) bond length is 2.05 Å. The V(4)-O(12) bond length is 2.05 Å. Both V(4)-O(11) bond lengths are 2.07 Å. Both V(4)-O(8) bond lengths are 2.06 Å. In the fifth V site, V(5) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent Zn(4)O4 tetrahedra, corners with three equivalent Zn(6)O4 tetrahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. All V(5)-O(7) bond lengths are 2.05 Å. All V(5)-O(8) bond lengths are 2.06 Å. In the sixth V site, V(6) is bonded to one O(5) and three equivalent O(11) atoms to form VO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent Zn(3)O6 octahedra, and corners with six equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-61°. The V(6)-O(5) bond length is 1.95 Å. All V(6)-O(11) bond lengths are 1.96 Å. There are six inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one O(10) and three equivalent O(1) atoms to form ZnO4 tetrahedra that share corners with three equivalent V(4)O6 octahedra, corners with three equivalent Zn(3)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-59°. The Zn(1)-O(10) bond length is 2.10 Å. All Zn(1)-O(1) bond lengths are 1.99 Å. In the second Zn site, Zn(2) is bonded to one O(2) and three equivalent O(4) atoms to form ZnO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. The Zn(2)-O(2) bond length is 1.99 Å. All Zn(2)-O(4) bond lengths are 2.02 Å. In the third Zn site, Zn(3) is bonded to three equivalent O(1) and three equivalent O(11) atoms to form ZnO6 octahedra that share corners with three equivalent V(6)O4 tetrahedra, corners with three equivalent Zn(1)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. All Zn(3)-O(1) bond lengths are 2.11 Å. All Zn(3)-O(11) bond lengths are 2.16 Å. In the fourth Zn site, Zn(4) is bonded to one O(6) and three equivalent O(8) atoms to form ZnO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and corners with six equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. The Zn(4)-O(6) bond length is 2.03 Å. All Zn(4)-O(8) bond lengths are 2.01 Å. In the fifth Zn site, Zn(5) is bonded to one O(9) and three equivalent O(3) atoms to form ZnO4 tetrahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(3)O6 octahedra, and corners with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. The Zn(5)-O(9) bond length is 2.04 Å. All Zn(5)-O(3) bond lengths are 2.01 Å. In the sixth Zn site, Zn(6) is bonded to one O(12) and three equivalent O(7) atoms to form ZnO4 tetrahedra that share corners with three equivalent V(4)O6 octahedra, corners with three equivalent V(5)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. The Zn(6)-O(12) bond length is 2.04 Å. All Zn(6)-O(7) bond lengths are 2.01 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to two equivalent V(1), one Zn(1), and one Zn(3) atom. In the second O site, O(2) is bonded to three equivalent V(1) and one Zn(2) atom to form distorted corner-sharing OV3Zn trigonal pyramids. In the third O site, O(3) is bonded to one V(3), two equivalent V(1), and one Zn(5) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the fourth O site, O(4) is bonded to one V(3), two equivalent V(2), and one Zn(2) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one V(6) and three equivalent V(1) atoms. In the sixth O site, O(6) is bonded to three equivalent V(2) and one Zn(4) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the seventh O site, O(7) is bonded to one V(5), two equivalent V(2), and one Zn(6) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the eighth O site, O(8) is bonded to one V(5), two equivalent V(4), and one Zn(4) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the ninth O site, O(9) is bonded to three equivalent V(2) and one Zn(5) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the tenth O site, O(10) is bonded to three equivalent V(4) and one Zn(1) atom to form a mixture of distorted corner and edge-sharing OV3Zn trigonal pyramids. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one V(6), two equivalent V(4), and one Zn(3) atom. In the twelfth O site, O(12) is bonded to three equivalent V(4) and one Zn(6) atom to form distorted corner-sharing OV3Zn trigonal pyramids.