Zn(Co2O3)2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Zn(1)O6 pentagonal pyramids, edges with five equivalent Co(1)O6 octahedra, and edges with five equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the second Co site, Co(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with four equivalent Zn(1)O6 pentagonal pyramids, edges with two equivalent Co(2)O6 octahedra, edges with five equivalent Co(1)O6 octahedra, and  an edgeedge with one Zn(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 0-61°. Zn(1) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form distorted ZnO6 pentagonal pyramids that share corners with four equivalent Co(1)O6 octahedra, corners with eight equivalent Co(2)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and faces with two equivalent Zn(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 29-71°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Co(2) and four equivalent Co(1) atoms to form OCo6 octahedra that share corners with four equivalent O(3)Co5 square pyramids, corners with two equivalent O(4)Zn2Co2 tetrahedra, edges with two equivalent O(1)Co6 octahedra, edges with six equivalent O(3)Co5 square pyramids, and edges with four equivalent O(2)Zn2Co3 trigonal bipyramids. In the second O site, O(2) is bonded to one Co(1), two equivalent Co(2), and two equivalent Zn(1) atoms to form distorted OZn2Co3 trigonal bipyramids that share corners with five equivalent O(3)Co5 square pyramids, corners with four equivalent O(4)Zn2Co2 tetrahedra, corners with two equivalent O(2)Zn2Co3 trigonal bipyramids, edges with two equivalent O(1)Co6 octahedra,  an edgeedge with one O(3)Co5 square pyramid,  an edgeedge with one O(4)Zn2Co2 tetrahedra, and edges with three equivalent O(2)Zn2Co3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Co(2) and three equivalent Co(1) atoms to form OCo5 square pyramids that share corners with two equivalent O(1)Co6 octahedra, corners with two equivalent O(4)Zn2Co2 tetrahedra, corners with five equivalent O(2)Zn2Co3 trigonal bipyramids, edges with three equivalent O(1)Co6 octahedra, edges with four equivalent O(3)Co5 square pyramids, and  an edgeedge with one O(2)Zn2Co3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 6°. In the fourth O site, O(4) is bonded to two equivalent Co(2) and two equivalent Zn(1) atoms to form OZn2Co2 tetrahedra that share corners with two equivalent O(1)Co6 octahedra, corners with four equivalent O(3)Co5 square pyramids, corners with two equivalent O(4)Zn2Co2 tetrahedra, corners with eight equivalent O(2)Zn2Co3 trigonal bipyramids, and edges with two equivalent O(2)Zn2Co3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 6°.
Zn(Co2O3)2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Zn(1)O6 pentagonal pyramids, edges with five equivalent Co(1)O6 octahedra, and edges with five equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-14°. The Co(1)-O(2) bond length is 1.92 Å. Both Co(1)-O(1) bond lengths are 2.11 Å. There is one shorter (1.97 Å) and two longer (2.07 Å) Co(1)-O(3) bond lengths. In the second Co site, Co(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form distorted CoO6 octahedra that share corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with four equivalent Zn(1)O6 pentagonal pyramids, edges with two equivalent Co(2)O6 octahedra, edges with five equivalent Co(1)O6 octahedra, and  an edgeedge with one Zn(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 0-61°. The Co(2)-O(1) bond length is 2.27 Å. The Co(2)-O(4) bond length is 1.95 Å. Both Co(2)-O(2) bond lengths are 2.07 Å. Both Co(2)-O(3) bond lengths are 2.14 Å. Zn(1) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form distorted ZnO6 pentagonal pyramids that share corners with four equivalent Co(1)O6 octahedra, corners with eight equivalent Co(2)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and faces with two equivalent Zn(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 29-71°. Both Zn(1)-O(4) bond lengths are 2.06 Å. All Zn(1)-O(2) bond lengths are 2.27 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Co(2) and four equivalent Co(1) atoms to form OCo6 octahedra that share corners with four equivalent O(3)Co5 square pyramids, corners with two equivalent O(4)Zn2Co2 tetrahedra, edges with two equivalent O(1)Co6 octahedra, edges with six equivalent O(3)Co5 square pyramids, and edges with four equivalent O(2)Zn2Co3 trigonal bipyramids. In the second O site, O(2) is bonded to one Co(1), two equivalent Co(2), and two equivalent Zn(1) atoms to form distorted OZn2Co3 trigonal bipyramids that share corners with five equivalent O(3)Co5 square pyramids, corners with four equivalent O(4)Zn2Co2 tetrahedra, corners with two equivalent O(2)Zn2Co3 trigonal bipyramids, edges with two equivalent O(1)Co6 octahedra,  an edgeedge with one O(3)Co5 square pyramid,  an edgeedge with one O(4)Zn2Co2 tetrahedra, and edges with three equivalent O(2)Zn2Co3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Co(2) and three equivalent Co(1) atoms to form OCo5 square pyramids that share corners with two equivalent O(1)Co6 octahedra, corners with two equivalent O(4)Zn2Co2 tetrahedra, corners with five equivalent O(2)Zn2Co3 trigonal bipyramids, edges with three equivalent O(1)Co6 octahedra, edges with four equivalent O(3)Co5 square pyramids, and  an edgeedge with one O(2)Zn2Co3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 6°. In the fourth O site, O(4) is bonded to two equivalent Co(2) and two equivalent Zn(1) atoms to form OZn2Co2 tetrahedra that share corners with two equivalent O(1)Co6 octahedra, corners with four equivalent O(3)Co5 square pyramids, corners with two equivalent O(4)Zn2Co2 tetrahedra, corners with eight equivalent O(2)Zn2Co3 trigonal bipyramids, and edges with two equivalent O(2)Zn2Co3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 6°.