V2ZnS4 is Spinel structured and crystallizes in the monoclinic Cm space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form VS6 octahedra that share corners with three equivalent Zn(1)S4 tetrahedra, corners with three equivalent Zn(2)S4 tetrahedra, edges with two equivalent V(1)S6 octahedra, edges with two equivalent V(2)S6 octahedra, and edges with two equivalent V(3)S6 octahedra. In the second V site, V(2) is bonded to one S(3), one S(5), two equivalent S(1), and two equivalent S(4) atoms to form VS6 octahedra that share corners with three equivalent Zn(1)S4 tetrahedra, corners with three equivalent Zn(2)S4 tetrahedra, edges with two equivalent V(3)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. In the third V site, V(3) is bonded to one S(2), one S(6), two equivalent S(1), and two equivalent S(4) atoms to form VS6 octahedra that share corners with three equivalent Zn(1)S4 tetrahedra, corners with three equivalent Zn(2)S4 tetrahedra, edges with two equivalent V(2)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(5), one S(6), and two equivalent S(1) atoms to form ZnS4 tetrahedra that share corners with three equivalent V(2)S6 octahedra, corners with three equivalent V(3)S6 octahedra, and corners with six equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 58-60°. In the second Zn site, Zn(2) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form ZnS4 tetrahedra that share corners with three equivalent V(2)S6 octahedra, corners with three equivalent V(3)S6 octahedra, and corners with six equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 56-57°. There are six inequivalent S sites. In the first S site, S(1) is bonded to one V(1), one V(2), one V(3), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing SV3Zn trigonal pyramids. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one V(3), two equivalent V(1), and one Zn(2) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one V(2), two equivalent V(1), and one Zn(2) atom. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one V(1), one V(2), one V(3), and one Zn(2) atom. In the fifth S site, S(5) is bonded to one V(2), two equivalent V(1), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing SV3Zn trigonal pyramids. In the sixth S site, S(6) is bonded to one V(3), two equivalent V(1), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing SV3Zn trigonal pyramids.
V2ZnS4 is Spinel structured and crystallizes in the monoclinic Cm space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one S(1), one S(2), one S(3), one S(4), one S(5), and one S(6) atom to form VS6 octahedra that share corners with three equivalent Zn(1)S4 tetrahedra, corners with three equivalent Zn(2)S4 tetrahedra, edges with two equivalent V(1)S6 octahedra, edges with two equivalent V(2)S6 octahedra, and edges with two equivalent V(3)S6 octahedra. The V(1)-S(1) bond length is 2.46 Å. The V(1)-S(2) bond length is 2.42 Å. The V(1)-S(3) bond length is 2.42 Å. The V(1)-S(4) bond length is 2.41 Å. The V(1)-S(5) bond length is 2.46 Å. The V(1)-S(6) bond length is 2.44 Å. In the second V site, V(2) is bonded to one S(3), one S(5), two equivalent S(1), and two equivalent S(4) atoms to form VS6 octahedra that share corners with three equivalent Zn(1)S4 tetrahedra, corners with three equivalent Zn(2)S4 tetrahedra, edges with two equivalent V(3)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. The V(2)-S(3) bond length is 2.41 Å. The V(2)-S(5) bond length is 2.47 Å. Both V(2)-S(1) bond lengths are 2.45 Å. Both V(2)-S(4) bond lengths are 2.40 Å. In the third V site, V(3) is bonded to one S(2), one S(6), two equivalent S(1), and two equivalent S(4) atoms to form VS6 octahedra that share corners with three equivalent Zn(1)S4 tetrahedra, corners with three equivalent Zn(2)S4 tetrahedra, edges with two equivalent V(2)S6 octahedra, and edges with four equivalent V(1)S6 octahedra. The V(3)-S(2) bond length is 2.43 Å. The V(3)-S(6) bond length is 2.45 Å. Both V(3)-S(1) bond lengths are 2.46 Å. Both V(3)-S(4) bond lengths are 2.41 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to one S(5), one S(6), and two equivalent S(1) atoms to form ZnS4 tetrahedra that share corners with three equivalent V(2)S6 octahedra, corners with three equivalent V(3)S6 octahedra, and corners with six equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 58-60°. The Zn(1)-S(5) bond length is 2.36 Å. The Zn(1)-S(6) bond length is 2.36 Å. Both Zn(1)-S(1) bond lengths are 2.36 Å. In the second Zn site, Zn(2) is bonded to one S(2), one S(3), and two equivalent S(4) atoms to form ZnS4 tetrahedra that share corners with three equivalent V(2)S6 octahedra, corners with three equivalent V(3)S6 octahedra, and corners with six equivalent V(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 56-57°. The Zn(2)-S(2) bond length is 2.31 Å. The Zn(2)-S(3) bond length is 2.33 Å. Both Zn(2)-S(4) bond lengths are 2.32 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one V(1), one V(2), one V(3), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing SV3Zn trigonal pyramids. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to one V(3), two equivalent V(1), and one Zn(2) atom. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one V(2), two equivalent V(1), and one Zn(2) atom. In the fourth S site, S(4) is bonded in a rectangular see-saw-like geometry to one V(1), one V(2), one V(3), and one Zn(2) atom. In the fifth S site, S(5) is bonded to one V(2), two equivalent V(1), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing SV3Zn trigonal pyramids. In the sixth S site, S(6) is bonded to one V(3), two equivalent V(1), and one Zn(1) atom to form a mixture of distorted corner and edge-sharing SV3Zn trigonal pyramids.