Rb2TmCl5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 10-coordinate geometry to two equivalent Cl(1), two equivalent Cl(3), two equivalent Cl(4), and four equivalent Cl(2) atoms. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to two equivalent Cl(1), two equivalent Cl(3), two equivalent Cl(4), and four equivalent Cl(2) atoms. Tm(1) is bonded to one Cl(1), one Cl(3), two equivalent Cl(2), and two equivalent Cl(4) atoms to form corner-sharing TmCl6 octahedra. The corner-sharing octahedra are not tilted. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), and one Tm(1) atom. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), and one Tm(1) atom. In the third Cl site, Cl(3) is bonded to two equivalent Rb(1), two equivalent Rb(2), and one Tm(1) atom to form distorted corner-sharing ClRb4Tm square pyramids. In the fourth Cl site, Cl(4) is bonded in a distorted linear geometry to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Tm(1) atoms.
Rb2TmCl5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 10-coordinate geometry to two equivalent Cl(1), two equivalent Cl(3), two equivalent Cl(4), and four equivalent Cl(2) atoms. There is one shorter (3.34 Å) and one longer (3.82 Å) Rb(1)-Cl(1) bond length. Both Rb(1)-Cl(3) bond lengths are 3.68 Å. Both Rb(1)-Cl(4) bond lengths are 3.79 Å. There are two shorter (3.41 Å) and two longer (3.57 Å) Rb(1)-Cl(2) bond lengths. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to two equivalent Cl(1), two equivalent Cl(3), two equivalent Cl(4), and four equivalent Cl(2) atoms. Both Rb(2)-Cl(1) bond lengths are 3.64 Å. There is one shorter (3.27 Å) and one longer (3.33 Å) Rb(2)-Cl(3) bond length. Both Rb(2)-Cl(4) bond lengths are 3.58 Å. There are two shorter (3.58 Å) and two longer (3.71 Å) Rb(2)-Cl(2) bond lengths. Tm(1) is bonded to one Cl(1), one Cl(3), two equivalent Cl(2), and two equivalent Cl(4) atoms to form corner-sharing TmCl6 octahedra. The corner-sharing octahedra are not tilted. The Tm(1)-Cl(1) bond length is 2.55 Å. The Tm(1)-Cl(3) bond length is 2.60 Å. Both Tm(1)-Cl(2) bond lengths are 2.52 Å. Both Tm(1)-Cl(4) bond lengths are 2.69 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Rb(2), and one Tm(1) atom. In the second Cl site, Cl(2) is bonded in a distorted single-bond geometry to two equivalent Rb(1), two equivalent Rb(2), and one Tm(1) atom. In the third Cl site, Cl(3) is bonded to two equivalent Rb(1), two equivalent Rb(2), and one Tm(1) atom to form distorted corner-sharing ClRb4Tm square pyramids. In the fourth Cl site, Cl(4) is bonded in a distorted linear geometry to two equivalent Rb(1), two equivalent Rb(2), and two equivalent Tm(1) atoms.