Ba2Co4ClO7 crystallizes in the trigonal R-3m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to three equivalent O(2), six equivalent O(1), and one Cl(1) atom. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to three equivalent O(1) and four equivalent Cl(1) atoms. There are four 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 corners with three equivalent Co(3)O6 octahedra, corners with three equivalent Co(2)O4 tetrahedra, and edges with three equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles are 11°. In the second Co site, Co(2) is bonded to one O(3) and three equivalent O(1) atoms to form corner-sharing CoO4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-59°. In the third Co site, Co(3) is bonded to six equivalent O(2) atoms to form a mixture of edge and corner-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles are 11°. In the fourth Co site, Co(4) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with two equivalent Co(2)O4 tetrahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with four equivalent Co(4)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ba(2), two equivalent Ba(1), one Co(1), and one Co(2) atom. In the second O site, O(2) is bonded to one Ba(1), one Co(1), one Co(3), and two equivalent Co(4) atoms to form distorted OBaCo4 trigonal bipyramids that share  a cornercorner with one Cl(1)Ba5 trigonal bipyramid, corners with three equivalent O(2)BaCo4 trigonal bipyramids, corners with two equivalent O(3)Co4 trigonal pyramids, edges with six equivalent O(2)BaCo4 trigonal bipyramids, and  an edgeedge with one O(3)Co4 trigonal pyramid. In the third O site, O(3) is bonded to one Co(2) and three equivalent Co(4) atoms to form distorted OCo4 trigonal pyramids that share corners with six equivalent O(2)BaCo4 trigonal bipyramids, corners with three equivalent O(3)Co4 trigonal pyramids, and edges with three equivalent O(2)BaCo4 trigonal bipyramids. Cl(1) is bonded to one Ba(1) and four equivalent Ba(2) atoms to form distorted ClBa5 trigonal bipyramids that share corners with three equivalent O(2)BaCo4 trigonal bipyramids, corners with six equivalent Cl(1)Ba5 trigonal bipyramids, and edges with three equivalent Cl(1)Ba5 trigonal bipyramids.
Ba2Co4ClO7 crystallizes in the trigonal R-3m space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to three equivalent O(2), six equivalent O(1), and one Cl(1) atom. All Ba(1)-O(2) bond lengths are 2.78 Å. All Ba(1)-O(1) bond lengths are 2.90 Å. The Ba(1)-Cl(1) bond length is 3.22 Å. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to three equivalent O(1) and four equivalent Cl(1) atoms. All Ba(2)-O(1) bond lengths are 2.57 Å. There is one shorter (3.27 Å) and three longer (3.41 Å) Ba(2)-Cl(1) bond lengths. There are four 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 corners with three equivalent Co(3)O6 octahedra, corners with three equivalent Co(2)O4 tetrahedra, and edges with three equivalent Co(4)O6 octahedra. The corner-sharing octahedral tilt angles are 11°. All Co(1)-O(1) bond lengths are 1.89 Å. All Co(1)-O(2) bond lengths are 2.14 Å. In the second Co site, Co(2) is bonded to one O(3) and three equivalent O(1) atoms to form corner-sharing CoO4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-59°. The Co(2)-O(3) bond length is 1.97 Å. All Co(2)-O(1) bond lengths are 1.89 Å. In the third Co site, Co(3) is bonded to six equivalent O(2) atoms to form a mixture of edge and corner-sharing CoO6 octahedra. The corner-sharing octahedral tilt angles are 11°. All Co(3)-O(2) bond lengths are 1.99 Å. In the fourth Co site, Co(4) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with two equivalent Co(2)O4 tetrahedra, edges with two equivalent Co(1)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with four equivalent Co(4)O6 octahedra. Both Co(4)-O(3) bond lengths are 1.93 Å. All Co(4)-O(2) bond lengths are 1.92 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Ba(2), two equivalent Ba(1), one Co(1), and one Co(2) atom. In the second O site, O(2) is bonded to one Ba(1), one Co(1), one Co(3), and two equivalent Co(4) atoms to form distorted OBaCo4 trigonal bipyramids that share  a cornercorner with one Cl(1)Ba5 trigonal bipyramid, corners with three equivalent O(2)BaCo4 trigonal bipyramids, corners with two equivalent O(3)Co4 trigonal pyramids, edges with six equivalent O(2)BaCo4 trigonal bipyramids, and  an edgeedge with one O(3)Co4 trigonal pyramid. In the third O site, O(3) is bonded to one Co(2) and three equivalent Co(4) atoms to form distorted OCo4 trigonal pyramids that share corners with six equivalent O(2)BaCo4 trigonal bipyramids, corners with three equivalent O(3)Co4 trigonal pyramids, and edges with three equivalent O(2)BaCo4 trigonal bipyramids. Cl(1) is bonded to one Ba(1) and four equivalent Ba(2) atoms to form distorted ClBa5 trigonal bipyramids that share corners with three equivalent O(2)BaCo4 trigonal bipyramids, corners with six equivalent Cl(1)Ba5 trigonal bipyramids, and edges with three equivalent Cl(1)Ba5 trigonal bipyramids.