VCr2O4 is Spinel structured and crystallizes in the triclinic P1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), and one O(7) atom to form VO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(2)O6 octahedra, corners with three equivalent Cr(3)O6 octahedra, and corners with three equivalent Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-62°. In the second V site, V(2) is bonded to one O(2), one O(5), one O(6), and one O(8) atom to form VO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(2)O6 octahedra, corners with three equivalent Cr(3)O6 octahedra, and corners with three equivalent Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-67°. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form CrO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(2)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with two equivalent Cr(4)O6 octahedra. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form CrO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with two equivalent Cr(4)O6 octahedra. In the third Cr site, Cr(3) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form CrO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Cr(4)O6 octahedra. In the fourth Cr site, Cr(4) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form CrO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(1), one Cr(2), one Cr(3), and one Cr(4) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one V(2), one Cr(1), one Cr(2), and one Cr(4) atom. In the third O site, O(3) is bonded to one V(1), one Cr(1), one Cr(2), and one Cr(3) atom to form a mixture of distorted corner and edge-sharing OVCr3 trigonal pyramids. In the fourth O site, O(4) is bonded to one V(1), one Cr(1), one Cr(3), and one Cr(4) atom to form a mixture of distorted corner and edge-sharing OVCr3 trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one V(2), one Cr(1), one Cr(3), and one Cr(4) atom. In the sixth O site, O(6) is bonded to one V(2), one Cr(1), one Cr(2), and one Cr(3) atom to form a mixture of distorted corner and edge-sharing OVCr3 trigonal pyramids. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one V(1), one Cr(1), one Cr(2), and one Cr(4) atom. In the eighth O site, O(8) is bonded to one V(2), one Cr(2), one Cr(3), and one Cr(4) atom to form a mixture of distorted corner and edge-sharing OVCr3 trigonal pyramids.
VCr2O4 is Spinel structured and crystallizes in the triclinic P1 space group. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(4), and one O(7) atom to form VO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(2)O6 octahedra, corners with three equivalent Cr(3)O6 octahedra, and corners with three equivalent Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-62°. The V(1)-O(1) bond length is 2.05 Å. The V(1)-O(3) bond length is 1.98 Å. The V(1)-O(4) bond length is 1.98 Å. The V(1)-O(7) bond length is 1.93 Å. In the second V site, V(2) is bonded to one O(2), one O(5), one O(6), and one O(8) atom to form VO4 tetrahedra that share corners with three equivalent Cr(1)O6 octahedra, corners with three equivalent Cr(2)O6 octahedra, corners with three equivalent Cr(3)O6 octahedra, and corners with three equivalent Cr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-67°. The V(2)-O(2) bond length is 2.00 Å. The V(2)-O(5) bond length is 2.05 Å. The V(2)-O(6) bond length is 2.05 Å. The V(2)-O(8) bond length is 2.08 Å. There are four inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form CrO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(2)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with two equivalent Cr(4)O6 octahedra. The Cr(1)-O(2) bond length is 2.32 Å. The Cr(1)-O(3) bond length is 2.09 Å. The Cr(1)-O(4) bond length is 2.09 Å. The Cr(1)-O(5) bond length is 2.07 Å. The Cr(1)-O(6) bond length is 2.07 Å. The Cr(1)-O(7) bond length is 2.32 Å. In the second Cr site, Cr(2) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form CrO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(3)O6 octahedra, and edges with two equivalent Cr(4)O6 octahedra. The Cr(2)-O(1) bond length is 2.10 Å. The Cr(2)-O(2) bond length is 2.00 Å. The Cr(2)-O(3) bond length is 2.07 Å. The Cr(2)-O(6) bond length is 2.02 Å. The Cr(2)-O(7) bond length is 2.08 Å. The Cr(2)-O(8) bond length is 2.04 Å. In the third Cr site, Cr(3) is bonded to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form CrO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Cr(4)O6 octahedra. The Cr(3)-O(1) bond length is 2.09 Å. The Cr(3)-O(3) bond length is 2.07 Å. The Cr(3)-O(4) bond length is 2.08 Å. The Cr(3)-O(5) bond length is 2.02 Å. The Cr(3)-O(6) bond length is 2.02 Å. The Cr(3)-O(8) bond length is 2.08 Å. In the fourth Cr site, Cr(4) is bonded to one O(1), one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form CrO6 octahedra that share corners with three equivalent V(1)O4 tetrahedra, corners with three equivalent V(2)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra, edges with two equivalent Cr(2)O6 octahedra, and edges with two equivalent Cr(3)O6 octahedra. The Cr(4)-O(1) bond length is 2.11 Å. The Cr(4)-O(2) bond length is 2.00 Å. The Cr(4)-O(4) bond length is 2.08 Å. The Cr(4)-O(5) bond length is 2.02 Å. The Cr(4)-O(7) bond length is 2.07 Å. The Cr(4)-O(8) bond length is 2.03 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one V(1), one Cr(2), one Cr(3), and one Cr(4) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one V(2), one Cr(1), one Cr(2), and one Cr(4) atom. In the third O site, O(3) is bonded to one V(1), one Cr(1), one Cr(2), and one Cr(3) atom to form a mixture of distorted corner and edge-sharing OVCr3 trigonal pyramids. In the fourth O site, O(4) is bonded to one V(1), one Cr(1), one Cr(3), and one Cr(4) atom to form a mixture of distorted corner and edge-sharing OVCr3 trigonal pyramids. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one V(2), one Cr(1), one Cr(3), and one Cr(4) atom. In the sixth O site, O(6) is bonded to one V(2), one Cr(1), one Cr(2), and one Cr(3) atom to form a mixture of distorted corner and edge-sharing OVCr3 trigonal pyramids. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one V(1), one Cr(1), one Cr(2), and one Cr(4) atom. In the eighth O site, O(8) is bonded to one V(2), one Cr(2), one Cr(3), and one Cr(4) atom to form a mixture of distorted corner and edge-sharing OVCr3 trigonal pyramids.