Cs5CoAgCl8 crystallizes in the orthorhombic Fmm2 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent Cl(2), two equivalent Cl(3), two equivalent Cl(7), and four equivalent Cl(1) atoms. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), one Cl(6), and two equivalent Cl(7) atoms. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one Cl(2), one Cl(5), two equivalent Cl(1), two equivalent Cl(4), and two equivalent Cl(7) atoms. In the fourth Cs site, Cs(4) is bonded in a 8-coordinate geometry to one Cl(3), one Cl(6), two equivalent Cl(1), two equivalent Cl(4), and two equivalent Cl(7) atoms. Co(1) is bonded in a tetrahedral geometry to one Cl(2), one Cl(3), and two equivalent Cl(1) atoms. Ag(1) is bonded in a 3-coordinate geometry to one Cl(4) and two equivalent Cl(7) atoms. There are seven inequivalent Cl sites. In the first Cl site, Cl(4) is bonded to two equivalent Cs(2), two equivalent Cs(3), two equivalent Cs(4), and one Ag(1) atom to form distorted ClCs6Ag pentagonal bipyramids that share corners with four equivalent Cl(7)Cs5Ag octahedra, edges with two equivalent Cl(7)Cs5Ag octahedra, edges with two equivalent Cl(5)Cs6 pentagonal pyramids, edges with two equivalent Cl(6)Cs6 pentagonal pyramids, faces with two equivalent Cl(7)Cs5Ag octahedra, and  a faceface with one Cl(4)Cs6Ag pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 43-44°. In the second Cl site, Cl(5) is bonded to two equivalent Cs(3) and four equivalent Cs(2) atoms to form distorted ClCs6 pentagonal pyramids that share corners with four equivalent Cl(7)Cs5Ag octahedra, edges with four equivalent Cl(7)Cs5Ag octahedra, edges with four equivalent Cl(4)Cs6Ag pentagonal bipyramids, and  a faceface with one Cl(6)Cs6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 43°. In the third Cl site, Cl(6) is bonded to two equivalent Cs(4) and four equivalent Cs(2) atoms to form distorted ClCs6 pentagonal pyramids that share corners with four equivalent Cl(7)Cs5Ag octahedra, edges with four equivalent Cl(7)Cs5Ag octahedra, edges with four equivalent Cl(4)Cs6Ag pentagonal bipyramids, and  a faceface with one Cl(5)Cs6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 44°. In the fourth Cl site, Cl(7) is bonded to one Cs(1), one Cs(3), one Cs(4), two equivalent Cs(2), and one Ag(1) atom to form distorted ClCs5Ag octahedra that share corners with six equivalent Cl(7)Cs5Ag octahedra, corners with two equivalent Cl(4)Cs6Ag pentagonal bipyramids,  a cornercorner with one Cl(5)Cs6 pentagonal pyramid,  a cornercorner with one Cl(6)Cs6 pentagonal pyramid,  an edgeedge with one Cl(4)Cs6Ag pentagonal bipyramid,  an edgeedge with one Cl(5)Cs6 pentagonal pyramid,  an edgeedge with one Cl(6)Cs6 pentagonal pyramid, and  a faceface with one Cl(4)Cs6Ag pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 1-42°. In the fifth Cl site, Cl(1) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), and one Co(1) atom. In the sixth Cl site, Cl(2) is bonded in a distorted single-bond geometry to one Cs(3), two equivalent Cs(1), two equivalent Cs(2), and one Co(1) atom. In the seventh Cl site, Cl(3) is bonded in a distorted single-bond geometry to one Cs(4), two equivalent Cs(1), two equivalent Cs(2), and one Co(1) atom.
Cs5CoAgCl8 crystallizes in the orthorhombic Fmm2 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent Cl(2), two equivalent Cl(3), two equivalent Cl(7), and four equivalent Cl(1) atoms. Both Cs(1)-Cl(2) bond lengths are 3.91 Å. Both Cs(1)-Cl(3) bond lengths are 3.91 Å. Both Cs(1)-Cl(7) bond lengths are 3.62 Å. There are two shorter (3.90 Å) and two longer (3.91 Å) Cs(1)-Cl(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), one Cl(6), and two equivalent Cl(7) atoms. The Cs(2)-Cl(1) bond length is 3.66 Å. The Cs(2)-Cl(2) bond length is 3.71 Å. The Cs(2)-Cl(3) bond length is 3.66 Å. The Cs(2)-Cl(4) bond length is 3.44 Å. The Cs(2)-Cl(5) bond length is 3.68 Å. The Cs(2)-Cl(6) bond length is 3.62 Å. There is one shorter (3.55 Å) and one longer (3.56 Å) Cs(2)-Cl(7) bond length. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to one Cl(2), one Cl(5), two equivalent Cl(1), two equivalent Cl(4), and two equivalent Cl(7) atoms. The Cs(3)-Cl(2) bond length is 3.65 Å. The Cs(3)-Cl(5) bond length is 3.43 Å. Both Cs(3)-Cl(1) bond lengths are 3.70 Å. Both Cs(3)-Cl(4) bond lengths are 3.75 Å. Both Cs(3)-Cl(7) bond lengths are 3.56 Å. In the fourth Cs site, Cs(4) is bonded in a 8-coordinate geometry to one Cl(3), one Cl(6), two equivalent Cl(1), two equivalent Cl(4), and two equivalent Cl(7) atoms. The Cs(4)-Cl(3) bond length is 3.64 Å. The Cs(4)-Cl(6) bond length is 3.44 Å. Both Cs(4)-Cl(1) bond lengths are 3.70 Å. Both Cs(4)-Cl(4) bond lengths are 3.61 Å. Both Cs(4)-Cl(7) bond lengths are 3.55 Å. Co(1) is bonded in a tetrahedral geometry to one Cl(2), one Cl(3), and two equivalent Cl(1) atoms. The Co(1)-Cl(2) bond length is 2.26 Å. The Co(1)-Cl(3) bond length is 2.27 Å. Both Co(1)-Cl(1) bond lengths are 2.27 Å. Ag(1) is bonded in a 3-coordinate geometry to one Cl(4) and two equivalent Cl(7) atoms. The Ag(1)-Cl(4) bond length is 3.09 Å. Both Ag(1)-Cl(7) bond lengths are 2.43 Å. There are seven inequivalent Cl sites. In the first Cl site, Cl(4) is bonded to two equivalent Cs(2), two equivalent Cs(3), two equivalent Cs(4), and one Ag(1) atom to form distorted ClCs6Ag pentagonal bipyramids that share corners with four equivalent Cl(7)Cs5Ag octahedra, edges with two equivalent Cl(7)Cs5Ag octahedra, edges with two equivalent Cl(5)Cs6 pentagonal pyramids, edges with two equivalent Cl(6)Cs6 pentagonal pyramids, faces with two equivalent Cl(7)Cs5Ag octahedra, and  a faceface with one Cl(4)Cs6Ag pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 43-44°. In the second Cl site, Cl(5) is bonded to two equivalent Cs(3) and four equivalent Cs(2) atoms to form distorted ClCs6 pentagonal pyramids that share corners with four equivalent Cl(7)Cs5Ag octahedra, edges with four equivalent Cl(7)Cs5Ag octahedra, edges with four equivalent Cl(4)Cs6Ag pentagonal bipyramids, and  a faceface with one Cl(6)Cs6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 43°. In the third Cl site, Cl(6) is bonded to two equivalent Cs(4) and four equivalent Cs(2) atoms to form distorted ClCs6 pentagonal pyramids that share corners with four equivalent Cl(7)Cs5Ag octahedra, edges with four equivalent Cl(7)Cs5Ag octahedra, edges with four equivalent Cl(4)Cs6Ag pentagonal bipyramids, and  a faceface with one Cl(5)Cs6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 44°. In the fourth Cl site, Cl(7) is bonded to one Cs(1), one Cs(3), one Cs(4), two equivalent Cs(2), and one Ag(1) atom to form distorted ClCs5Ag octahedra that share corners with six equivalent Cl(7)Cs5Ag octahedra, corners with two equivalent Cl(4)Cs6Ag pentagonal bipyramids,  a cornercorner with one Cl(5)Cs6 pentagonal pyramid,  a cornercorner with one Cl(6)Cs6 pentagonal pyramid,  an edgeedge with one Cl(4)Cs6Ag pentagonal bipyramid,  an edgeedge with one Cl(5)Cs6 pentagonal pyramid,  an edgeedge with one Cl(6)Cs6 pentagonal pyramid, and  a faceface with one Cl(4)Cs6Ag pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 1-42°. In the fifth Cl site, Cl(1) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(3), one Cs(4), two equivalent Cs(1), and one Co(1) atom. In the sixth Cl site, Cl(2) is bonded in a distorted single-bond geometry to one Cs(3), two equivalent Cs(1), two equivalent Cs(2), and one Co(1) atom. In the seventh Cl site, Cl(3) is bonded in a distorted single-bond geometry to one Cs(4), two equivalent Cs(1), two equivalent Cs(2), and one Co(1) atom.