CdCoO3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CoO6 octahedra that share corners with six equivalent Cd(1)O5 trigonal bipyramids, edges with three equivalent Co(2)O6 octahedra, and edges with two equivalent Cd(1)O5 trigonal bipyramids. In the second Co site, Co(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with eight equivalent Cd(1)O5 trigonal bipyramids, edges with two equivalent Co(2)O6 octahedra, and edges with three equivalent Co(1)O6 octahedra. Cd(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CdO5 trigonal bipyramids that share corners with three equivalent Co(1)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, corners with two equivalent Cd(1)O5 trigonal bipyramids,  an edgeedge with one Co(1)O6 octahedra, and  an edgeedge with one Cd(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 28-75°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Co(1), two equivalent Co(2), and one Cd(1) atom to form distorted OCdCo3 trigonal pyramids that share corners with three equivalent O(1)CdCo3 trigonal pyramids, corners with four equivalent O(3)Cd2Co2 trigonal pyramids, edges with two equivalent O(3)Cd2Co2 trigonal pyramids, and edges with two equivalent O(1)CdCo3 trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Co(1) and two equivalent Cd(1) atoms. In the third O site, O(3) is bonded to one Co(1), one Co(2), and two equivalent Cd(1) atoms to form distorted OCd2Co2 trigonal pyramids that share corners with two equivalent O(3)Cd2Co2 trigonal pyramids, corners with four equivalent O(1)CdCo3 trigonal pyramids,  an edgeedge with one O(3)Cd2Co2 trigonal pyramid, and edges with two equivalent O(1)CdCo3 trigonal pyramids.
CdCoO3 crystallizes in the monoclinic C2/c space group. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CoO6 octahedra that share corners with six equivalent Cd(1)O5 trigonal bipyramids, edges with three equivalent Co(2)O6 octahedra, and edges with two equivalent Cd(1)O5 trigonal bipyramids. Both Co(1)-O(1) bond lengths are 2.06 Å. Both Co(1)-O(2) bond lengths are 1.78 Å. Both Co(1)-O(3) bond lengths are 2.05 Å. In the second Co site, Co(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with eight equivalent Cd(1)O5 trigonal bipyramids, edges with two equivalent Co(2)O6 octahedra, and edges with three equivalent Co(1)O6 octahedra. Both Co(2)-O(3) bond lengths are 1.83 Å. There are two shorter (1.92 Å) and two longer (1.95 Å) Co(2)-O(1) bond lengths. Cd(1) is bonded to one O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted CdO5 trigonal bipyramids that share corners with three equivalent Co(1)O6 octahedra, corners with four equivalent Co(2)O6 octahedra, corners with two equivalent Cd(1)O5 trigonal bipyramids,  an edgeedge with one Co(1)O6 octahedra, and  an edgeedge with one Cd(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 28-75°. The Cd(1)-O(1) bond length is 2.39 Å. There is one shorter (2.22 Å) and one longer (2.29 Å) Cd(1)-O(2) bond length. There is one shorter (2.20 Å) and one longer (2.38 Å) Cd(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Co(1), two equivalent Co(2), and one Cd(1) atom to form distorted OCdCo3 trigonal pyramids that share corners with three equivalent O(1)CdCo3 trigonal pyramids, corners with four equivalent O(3)Cd2Co2 trigonal pyramids, edges with two equivalent O(3)Cd2Co2 trigonal pyramids, and edges with two equivalent O(1)CdCo3 trigonal pyramids. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Co(1) and two equivalent Cd(1) atoms. In the third O site, O(3) is bonded to one Co(1), one Co(2), and two equivalent Cd(1) atoms to form distorted OCd2Co2 trigonal pyramids that share corners with two equivalent O(3)Cd2Co2 trigonal pyramids, corners with four equivalent O(1)CdCo3 trigonal pyramids,  an edgeedge with one O(3)Cd2Co2 trigonal pyramid, and edges with two equivalent O(1)CdCo3 trigonal pyramids.