Cs2AuAgCl6 crystallizes in the tetragonal I4/mmm space group. Cs(1) is bonded to four equivalent Cl(1) and eight equivalent Cl(2) atoms to form distorted CsCl12 cuboctahedra that share corners with twelve equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with four equivalent Ag(1)Cl6 octahedra. Au(1) is bonded in a square co-planar geometry to four equivalent Cl(2) atoms. Ag(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form AgCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Ag(1) atom. In the second Cl site, Cl(2) is bonded to four equivalent Cs(1), one Au(1), and one Ag(1) atom to form a mixture of distorted edge, face, and corner-sharing ClCs4AgAu octahedra. The corner-sharing octahedral tilt angles range from 0-57°.
Cs2AuAgCl6 crystallizes in the tetragonal I4/mmm space group. Cs(1) is bonded to four equivalent Cl(1) and eight equivalent Cl(2) atoms to form distorted CsCl12 cuboctahedra that share corners with twelve equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with four equivalent Ag(1)Cl6 octahedra. All Cs(1)-Cl(1) bond lengths are 3.76 Å. All Cs(1)-Cl(2) bond lengths are 3.90 Å. Au(1) is bonded in a square co-planar geometry to four equivalent Cl(2) atoms. All Au(1)-Cl(2) bond lengths are 2.36 Å. Ag(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form AgCl6 octahedra that share faces with eight equivalent Cs(1)Cl12 cuboctahedra. Both Ag(1)-Cl(1) bond lengths are 2.40 Å. All Ag(1)-Cl(2) bond lengths are 2.91 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a distorted single-bond geometry to four equivalent Cs(1) and one Ag(1) atom. In the second Cl site, Cl(2) is bonded to four equivalent Cs(1), one Au(1), and one Ag(1) atom to form a mixture of distorted edge, face, and corner-sharing ClCs4AgAu octahedra. The corner-sharing octahedral tilt angles range from 0-57°.