Rb2AgCl3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one Cl(1), two equivalent Cl(3), and four equivalent Cl(2) atoms. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to one Cl(2), three equivalent Cl(1), and three equivalent Cl(3) atoms. Ag(1) is bonded to one Cl(2), one Cl(3), and two equivalent Cl(1) atoms to form corner-sharing AgCl4 tetrahedra. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to one Rb(1), three equivalent Rb(2), and two equivalent Ag(1) atoms. In the second Cl site, Cl(2) is bonded to one Rb(2), four equivalent Rb(1), and one Ag(1) atom to form a mixture of edge, corner, and face-sharing ClRb5Ag octahedra. The corner-sharing octahedral tilt angles range from 23-55°. In the third Cl site, Cl(3) is bonded to two equivalent Rb(1), three equivalent Rb(2), and one Ag(1) atom to form a mixture of distorted edge, corner, and face-sharing ClRb5Ag octahedra. The corner-sharing octahedral tilt angles range from 52-55°.
Rb2AgCl3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one Cl(1), two equivalent Cl(3), and four equivalent Cl(2) atoms. The Rb(1)-Cl(1) bond length is 3.44 Å. Both Rb(1)-Cl(3) bond lengths are 3.39 Å. All Rb(1)-Cl(2) bond lengths are 3.31 Å. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to one Cl(2), three equivalent Cl(1), and three equivalent Cl(3) atoms. The Rb(2)-Cl(2) bond length is 3.32 Å. There are two shorter (3.38 Å) and one longer (3.52 Å) Rb(2)-Cl(1) bond length. There are two shorter (3.25 Å) and one longer (3.38 Å) Rb(2)-Cl(3) bond length. Ag(1) is bonded to one Cl(2), one Cl(3), and two equivalent Cl(1) atoms to form corner-sharing AgCl4 tetrahedra. The Ag(1)-Cl(2) bond length is 2.60 Å. The Ag(1)-Cl(3) bond length is 2.58 Å. Both Ag(1)-Cl(1) bond lengths are 2.61 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 6-coordinate geometry to one Rb(1), three equivalent Rb(2), and two equivalent Ag(1) atoms. In the second Cl site, Cl(2) is bonded to one Rb(2), four equivalent Rb(1), and one Ag(1) atom to form a mixture of edge, corner, and face-sharing ClRb5Ag octahedra. The corner-sharing octahedral tilt angles range from 23-55°. In the third Cl site, Cl(3) is bonded to two equivalent Rb(1), three equivalent Rb(2), and one Ag(1) atom to form a mixture of distorted edge, corner, and face-sharing ClRb5Ag octahedra. The corner-sharing octahedral tilt angles range from 52-55°.