ZnCo2O4 is Spinel-like structured and crystallizes in the trigonal P3m1 space group. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form CoO6 octahedra that share  a cornercorner with one Co(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 Co(3)O6 octahedra,  an edgeedge with one Zn(3)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. In the second Co site, Co(2) is bonded to one O(6), one O(9), two equivalent O(4), and two equivalent O(7) atoms to form CoO6 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 Co(3)O6 octahedra,  an edgeedge with one Co(5)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. In the third Co site, Co(3) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form CoO6 octahedra that share corners with three equivalent Zn(2)O4 tetrahedra, corners with three equivalent Zn(5)O4 tetrahedra, edges with three equivalent Co(1)O6 octahedra, and edges with three equivalent Co(2)O6 octahedra. In the fourth Co site, Co(4) is bonded to one O(10), one O(12), two equivalent O(11), and two equivalent O(8) atoms to form CoO6 octahedra that share  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one Zn(6)O4 tetrahedra, corners with two equivalent Co(6)O4 tetrahedra, corners with two equivalent Zn(4)O4 tetrahedra,  an edgeedge with one Co(5)O6 octahedra,  an edgeedge with one Zn(3)O6 octahedra, and edges with four equivalent Co(4)O6 octahedra. In the fifth Co site, Co(5) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form CoO6 octahedra that share corners with three equivalent Zn(4)O4 tetrahedra, corners with three equivalent Zn(6)O4 tetrahedra, edges with three equivalent Co(2)O6 octahedra, and edges with three equivalent Co(4)O6 octahedra. In the sixth Co site, Co(6) is bonded to one O(5) and three equivalent O(11) atoms to form CoO4 tetrahedra that share corners with three equivalent Co(1)O6 octahedra, corners with three equivalent Zn(3)O6 octahedra, and corners with six equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. 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 Co(4)O6 octahedra, corners with three equivalent Zn(3)O6 octahedra, and corners with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-63°. 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 Co(1)O6 octahedra, corners with three equivalent Co(3)O6 octahedra, and corners with six equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-60°. 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 Co(6)O4 tetrahedra, corners with three equivalent Zn(1)O4 tetrahedra, edges with three equivalent Co(1)O6 octahedra, and edges with three equivalent Co(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 Co(2)O6 octahedra, corners with three equivalent Co(5)O6 octahedra, and corners with six equivalent Co(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 Co(2)O6 octahedra, corners with three equivalent Co(3)O6 octahedra, and corners with six equivalent Co(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 Co(4)O6 octahedra, corners with three equivalent Co(5)O6 octahedra, and corners with six equivalent Co(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 Co(1), one Zn(1), and one Zn(3) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Co(1) and one Zn(2) atom. In the third O site, O(3) is bonded to one Co(3), two equivalent Co(1), and one Zn(5) atom to form distorted OZnCo3 trigonal pyramids that share  a cornercorner with one O(9)ZnCo3 trigonal pyramid, corners with two equivalent O(3)ZnCo3 trigonal pyramids, corners with three equivalent O(4)ZnCo3 trigonal pyramids,  an edgeedge with one O(5)Co4 trigonal pyramid, and edges with two equivalent O(3)ZnCo3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Co(3), two equivalent Co(2), and one Zn(2) atom to form a mixture of distorted edge and corner-sharing OZnCo3 trigonal pyramids. In the fifth O site, O(5) is bonded to one Co(6) and three equivalent Co(1) atoms to form distorted edge-sharing OCo4 trigonal pyramids. In the sixth O site, O(6) is bonded to three equivalent Co(2) and one Zn(4) atom to form a mixture of distorted edge and corner-sharing OZnCo3 trigonal pyramids. In the seventh O site, O(7) is bonded to one Co(5), two equivalent Co(2), and one Zn(6) atom to form a mixture of distorted edge and corner-sharing OZnCo3 trigonal pyramids. In the eighth O site, O(8) is bonded to one Co(5), two equivalent Co(4), and one Zn(4) atom to form a mixture of distorted edge and corner-sharing OZnCo3 trigonal pyramids. In the ninth O site, O(9) is bonded to three equivalent Co(2) and one Zn(5) atom to form a mixture of distorted edge and corner-sharing OZnCo3 trigonal pyramids. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Co(4) and one Zn(1) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Co(6), two equivalent Co(4), and one Zn(3) atom. In the twelfth O site, O(12) is bonded to three equivalent Co(4) and one Zn(6) atom to form distorted corner-sharing OZnCo3 trigonal pyramids.
ZnCo2O4 is Spinel-like structured and crystallizes in the trigonal P3m1 space group. There are six inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form CoO6 octahedra that share  a cornercorner with one Co(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 Co(3)O6 octahedra,  an edgeedge with one Zn(3)O6 octahedra, and edges with four equivalent Co(1)O6 octahedra. The Co(1)-O(2) bond length is 2.03 Å. The Co(1)-O(5) bond length is 2.05 Å. Both Co(1)-O(1) bond lengths are 1.97 Å. Both Co(1)-O(3) bond lengths are 2.03 Å. In the second Co site, Co(2) is bonded to one O(6), one O(9), two equivalent O(4), and two equivalent O(7) atoms to form CoO6 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 Co(3)O6 octahedra,  an edgeedge with one Co(5)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The Co(2)-O(6) bond length is 2.02 Å. The Co(2)-O(9) bond length is 2.03 Å. Both Co(2)-O(4) bond lengths are 2.01 Å. Both Co(2)-O(7) bond lengths are 2.02 Å. In the third Co site, Co(3) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form CoO6 octahedra that share corners with three equivalent Zn(2)O4 tetrahedra, corners with three equivalent Zn(5)O4 tetrahedra, edges with three equivalent Co(1)O6 octahedra, and edges with three equivalent Co(2)O6 octahedra. All Co(3)-O(3) bond lengths are 2.00 Å. All Co(3)-O(4) bond lengths are 2.06 Å. In the fourth Co site, Co(4) is bonded to one O(10), one O(12), two equivalent O(11), and two equivalent O(8) atoms to form CoO6 octahedra that share  a cornercorner with one Zn(1)O4 tetrahedra,  a cornercorner with one Zn(6)O4 tetrahedra, corners with two equivalent Co(6)O4 tetrahedra, corners with two equivalent Zn(4)O4 tetrahedra,  an edgeedge with one Co(5)O6 octahedra,  an edgeedge with one Zn(3)O6 octahedra, and edges with four equivalent Co(4)O6 octahedra. The Co(4)-O(10) bond length is 2.04 Å. The Co(4)-O(12) bond length is 2.03 Å. Both Co(4)-O(11) bond lengths are 2.00 Å. Both Co(4)-O(8) bond lengths are 2.02 Å. In the fifth Co site, Co(5) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form CoO6 octahedra that share corners with three equivalent Zn(4)O4 tetrahedra, corners with three equivalent Zn(6)O4 tetrahedra, edges with three equivalent Co(2)O6 octahedra, and edges with three equivalent Co(4)O6 octahedra. All Co(5)-O(7) bond lengths are 2.03 Å. All Co(5)-O(8) bond lengths are 2.01 Å. In the sixth Co site, Co(6) is bonded to one O(5) and three equivalent O(11) atoms to form CoO4 tetrahedra that share corners with three equivalent Co(1)O6 octahedra, corners with three equivalent Zn(3)O6 octahedra, and corners with six equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-62°. The Co(6)-O(5) bond length is 1.97 Å. All Co(6)-O(11) bond lengths are 1.95 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 Co(4)O6 octahedra, corners with three equivalent Zn(3)O6 octahedra, and corners with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-63°. The Zn(1)-O(10) bond length is 1.97 Å. All Zn(1)-O(1) bond lengths are 1.97 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 Co(1)O6 octahedra, corners with three equivalent Co(3)O6 octahedra, and corners with six equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-60°. The Zn(2)-O(2) bond length is 1.96 Å. All Zn(2)-O(4) bond lengths are 1.98 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 Co(6)O4 tetrahedra, corners with three equivalent Zn(1)O4 tetrahedra, edges with three equivalent Co(1)O6 octahedra, and edges with three equivalent Co(4)O6 octahedra. All Zn(3)-O(1) bond lengths are 2.12 Å. All Zn(3)-O(11) bond lengths are 2.13 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 Co(2)O6 octahedra, corners with three equivalent Co(5)O6 octahedra, and corners with six equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. The Zn(4)-O(6) bond length is 1.98 Å. All Zn(4)-O(8) bond lengths are 1.98 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 Co(2)O6 octahedra, corners with three equivalent Co(3)O6 octahedra, and corners with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. The Zn(5)-O(9) bond length is 1.98 Å. All Zn(5)-O(3) bond lengths are 1.99 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 Co(4)O6 octahedra, corners with three equivalent Co(5)O6 octahedra, and corners with six equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-59°. The Zn(6)-O(12) bond length is 1.96 Å. All Zn(6)-O(7) bond lengths are 1.98 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 Co(1), one Zn(1), and one Zn(3) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Co(1) and one Zn(2) atom. In the third O site, O(3) is bonded to one Co(3), two equivalent Co(1), and one Zn(5) atom to form distorted OZnCo3 trigonal pyramids that share  a cornercorner with one O(9)ZnCo3 trigonal pyramid, corners with two equivalent O(3)ZnCo3 trigonal pyramids, corners with three equivalent O(4)ZnCo3 trigonal pyramids,  an edgeedge with one O(5)Co4 trigonal pyramid, and edges with two equivalent O(3)ZnCo3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Co(3), two equivalent Co(2), and one Zn(2) atom to form a mixture of distorted edge and corner-sharing OZnCo3 trigonal pyramids. In the fifth O site, O(5) is bonded to one Co(6) and three equivalent Co(1) atoms to form distorted edge-sharing OCo4 trigonal pyramids. In the sixth O site, O(6) is bonded to three equivalent Co(2) and one Zn(4) atom to form a mixture of distorted edge and corner-sharing OZnCo3 trigonal pyramids. In the seventh O site, O(7) is bonded to one Co(5), two equivalent Co(2), and one Zn(6) atom to form a mixture of distorted edge and corner-sharing OZnCo3 trigonal pyramids. In the eighth O site, O(8) is bonded to one Co(5), two equivalent Co(4), and one Zn(4) atom to form a mixture of distorted edge and corner-sharing OZnCo3 trigonal pyramids. In the ninth O site, O(9) is bonded to three equivalent Co(2) and one Zn(5) atom to form a mixture of distorted edge and corner-sharing OZnCo3 trigonal pyramids. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Co(4) and one Zn(1) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Co(6), two equivalent Co(4), and one Zn(3) atom. In the twelfth O site, O(12) is bonded to three equivalent Co(4) and one Zn(6) atom to form distorted corner-sharing OZnCo3 trigonal pyramids.