Ca6Sc(CoO4)3 crystallizes in the trigonal R32 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to four equivalent O(1) and four equivalent O(2) atoms. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to four equivalent O(1) and four equivalent O(2) atoms. Sc(1) is bonded to six equivalent O(2) atoms to form distorted ScO6 pentagonal pyramids that share faces with two equivalent Co(1)O6 octahedra. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form CoO6 octahedra that share  a faceface with one Sc(1)O6 pentagonal pyramid and  a faceface with one Co(2)O6 pentagonal pyramid. In the second Co site, Co(2) is bonded to six equivalent O(1) atoms to form distorted face-sharing CoO6 pentagonal pyramids. There are two inequivalent O sites. In the first O site, O(2) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Sc(1), and one Co(1) atom to form distorted OCa4ScCo octahedra that share corners with seven equivalent O(1)Ca4Co2 octahedra, corners with eight equivalent O(2)Ca4ScCo octahedra,  an edgeedge with one O(2)Ca4ScCo octahedra, edges with three equivalent O(1)Ca4Co2 octahedra, faces with two equivalent O(1)Ca4Co2 octahedra, and faces with three equivalent O(2)Ca4ScCo octahedra. The corner-sharing octahedral tilt angles range from 1-67°. In the second O site, O(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Co(1), and one Co(2) atom to form distorted OCa4Co2 octahedra that share corners with seven equivalent O(2)Ca4ScCo octahedra, corners with eight equivalent O(1)Ca4Co2 octahedra,  an edgeedge with one O(1)Ca4Co2 octahedra, edges with three equivalent O(2)Ca4ScCo octahedra, faces with two equivalent O(2)Ca4ScCo octahedra, and faces with three equivalent O(1)Ca4Co2 octahedra. The corner-sharing octahedral tilt angles range from 1-67°.
Ca6Sc(CoO4)3 crystallizes in the trigonal R32 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 8-coordinate geometry to four equivalent O(1) and four equivalent O(2) atoms. There are two shorter (2.33 Å) and two longer (2.56 Å) Ca(1)-O(1) bond lengths. There are two shorter (2.54 Å) and two longer (2.66 Å) Ca(1)-O(2) bond lengths. In the second Ca site, Ca(2) is bonded in a 8-coordinate geometry to four equivalent O(1) and four equivalent O(2) atoms. There are two shorter (2.56 Å) and two longer (2.63 Å) Ca(2)-O(1) bond lengths. There are two shorter (2.35 Å) and two longer (2.51 Å) Ca(2)-O(2) bond lengths. Sc(1) is bonded to six equivalent O(2) atoms to form distorted ScO6 pentagonal pyramids that share faces with two equivalent Co(1)O6 octahedra. All Sc(1)-O(2) bond lengths are 2.15 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form CoO6 octahedra that share  a faceface with one Sc(1)O6 pentagonal pyramid and  a faceface with one Co(2)O6 pentagonal pyramid. All Co(1)-O(1) bond lengths are 2.00 Å. All Co(1)-O(2) bond lengths are 2.01 Å. In the second Co site, Co(2) is bonded to six equivalent O(1) atoms to form distorted face-sharing CoO6 pentagonal pyramids. All Co(2)-O(1) bond lengths are 2.11 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Sc(1), and one Co(1) atom to form distorted OCa4ScCo octahedra that share corners with seven equivalent O(1)Ca4Co2 octahedra, corners with eight equivalent O(2)Ca4ScCo octahedra,  an edgeedge with one O(2)Ca4ScCo octahedra, edges with three equivalent O(1)Ca4Co2 octahedra, faces with two equivalent O(1)Ca4Co2 octahedra, and faces with three equivalent O(2)Ca4ScCo octahedra. The corner-sharing octahedral tilt angles range from 1-67°. In the second O site, O(1) is bonded to two equivalent Ca(1), two equivalent Ca(2), one Co(1), and one Co(2) atom to form distorted OCa4Co2 octahedra that share corners with seven equivalent O(2)Ca4ScCo octahedra, corners with eight equivalent O(1)Ca4Co2 octahedra,  an edgeedge with one O(1)Ca4Co2 octahedra, edges with three equivalent O(2)Ca4ScCo octahedra, faces with two equivalent O(2)Ca4ScCo octahedra, and faces with three equivalent O(1)Ca4Co2 octahedra. The corner-sharing octahedral tilt angles range from 1-67°.