Ba5Co5ClO13 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 12-coordinate geometry to three equivalent O(3) and nine equivalent O(2) atoms. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to three equivalent O(2), six equivalent O(3), and one Cl(1) atom. In the third Ba site, Ba(3) is bonded to three equivalent O(1), six equivalent O(3), and three equivalent Cl(1) atoms to form BaCl3O9 cuboctahedra that share edges with six equivalent Ba(3)Cl3O9 cuboctahedra, edges with six equivalent Co(1)O4 tetrahedra, and faces with two equivalent Co(3)O6 octahedra. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1) and three equivalent O(3) atoms to form CoO4 tetrahedra that share corners with three equivalent Co(3)O6 octahedra,  a cornercorner with one Co(1)O4 tetrahedra, and edges with three equivalent Ba(3)Cl3O9 cuboctahedra. The corner-sharing octahedral tilt angles are 11°. In the second Co site, Co(2) is bonded to six equivalent O(2) atoms to form face-sharing CoO6 octahedra. In the third Co site, Co(3) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form CoO6 octahedra that share corners with three equivalent Co(1)O4 tetrahedra,  a faceface with one Ba(3)Cl3O9 cuboctahedra, and  a faceface with one Co(2)O6 octahedra. There are three inequivalent O sites. In the first O site, O(3) is bonded in a distorted linear geometry to one Ba(1), one Ba(3), two equivalent Ba(2), one Co(1), and one Co(3) atom. In the second O site, O(1) is bonded in a linear geometry to three equivalent Ba(3) and two equivalent Co(1) atoms. In the third O site, O(2) is bonded to one Ba(2), three equivalent Ba(1), one Co(2), and one Co(3) atom to form distorted OBa4Co2 octahedra that share corners with eleven equivalent O(2)Ba4Co2 octahedra,  a cornercorner with one Cl(1)Ba5 trigonal bipyramid, edges with two equivalent O(2)Ba4Co2 octahedra, and faces with six equivalent O(2)Ba4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. Cl(1) is bonded to two equivalent Ba(2) and three equivalent Ba(3) atoms to form ClBa5 trigonal bipyramids that share corners with six equivalent O(2)Ba4Co2 octahedra and corners with six equivalent Cl(1)Ba5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 43°.
Ba5Co5ClO13 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 12-coordinate geometry to three equivalent O(3) and nine equivalent O(2) atoms. All Ba(1)-O(3) bond lengths are 3.17 Å. There are three shorter (2.86 Å) and six longer (2.90 Å) Ba(1)-O(2) bond lengths. In the second Ba site, Ba(2) is bonded in a 10-coordinate geometry to three equivalent O(2), six equivalent O(3), and one Cl(1) atom. All Ba(2)-O(2) bond lengths are 2.70 Å. All Ba(2)-O(3) bond lengths are 2.94 Å. The Ba(2)-Cl(1) bond length is 3.05 Å. In the third Ba site, Ba(3) is bonded to three equivalent O(1), six equivalent O(3), and three equivalent Cl(1) atoms to form BaCl3O9 cuboctahedra that share edges with six equivalent Ba(3)Cl3O9 cuboctahedra, edges with six equivalent Co(1)O4 tetrahedra, and faces with two equivalent Co(3)O6 octahedra. All Ba(3)-O(1) bond lengths are 3.34 Å. All Ba(3)-O(3) bond lengths are 3.01 Å. All Ba(3)-Cl(1) bond lengths are 3.34 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(1) and three equivalent O(3) atoms to form CoO4 tetrahedra that share corners with three equivalent Co(3)O6 octahedra,  a cornercorner with one Co(1)O4 tetrahedra, and edges with three equivalent Ba(3)Cl3O9 cuboctahedra. The corner-sharing octahedral tilt angles are 11°. The Co(1)-O(1) bond length is 1.82 Å. All Co(1)-O(3) bond lengths are 1.86 Å. In the second Co site, Co(2) is bonded to six equivalent O(2) atoms to form face-sharing CoO6 octahedra. All Co(2)-O(2) bond lengths are 1.90 Å. In the third Co site, Co(3) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form CoO6 octahedra that share corners with three equivalent Co(1)O4 tetrahedra,  a faceface with one Ba(3)Cl3O9 cuboctahedra, and  a faceface with one Co(2)O6 octahedra. All Co(3)-O(2) bond lengths are 2.03 Å. All Co(3)-O(3) bond lengths are 1.97 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded in a distorted linear geometry to one Ba(1), one Ba(3), two equivalent Ba(2), one Co(1), and one Co(3) atom. In the second O site, O(1) is bonded in a linear geometry to three equivalent Ba(3) and two equivalent Co(1) atoms. In the third O site, O(2) is bonded to one Ba(2), three equivalent Ba(1), one Co(2), and one Co(3) atom to form distorted OBa4Co2 octahedra that share corners with eleven equivalent O(2)Ba4Co2 octahedra,  a cornercorner with one Cl(1)Ba5 trigonal bipyramid, edges with two equivalent O(2)Ba4Co2 octahedra, and faces with six equivalent O(2)Ba4Co2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. Cl(1) is bonded to two equivalent Ba(2) and three equivalent Ba(3) atoms to form ClBa5 trigonal bipyramids that share corners with six equivalent O(2)Ba4Co2 octahedra and corners with six equivalent Cl(1)Ba5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 43°.