Rb3TmCl6 crystallizes in the monoclinic C2/c space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one Cl(1), one Cl(2), one Cl(3), two equivalent Cl(4), and two equivalent Cl(5) atoms. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one Cl(2), one Cl(3), one Cl(4), one Cl(5), two equivalent Cl(1), and two equivalent Cl(6) atoms. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one Cl(1), one Cl(2), one Cl(4), one Cl(5), two equivalent Cl(3), and two equivalent Cl(6) atoms. There are two inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in an octahedral geometry to two equivalent Cl(2), two equivalent Cl(4), and two equivalent Cl(5) atoms. In the second Tm site, Tm(2) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(3), and two equivalent Cl(6) atoms. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(2), and one Tm(2) atom. In the second Cl site, Cl(2) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(2), one Rb(3), and one Tm(1) atom. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), two equivalent Rb(3), and one Tm(2) atom. In the fourth Cl site, Cl(4) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Tm(1) atom to form a mixture of distorted edge, face, and corner-sharing ClRb4Tm square pyramids. In the fifth Cl site, Cl(5) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Tm(1) atom to form a mixture of distorted edge, face, and corner-sharing ClRb4Tm square pyramids. In the sixth Cl site, Cl(6) is bonded in a 5-coordinate geometry to two equivalent Rb(2), two equivalent Rb(3), and one Tm(2) atom.
Rb3TmCl6 crystallizes in the monoclinic C2/c space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one Cl(1), one Cl(2), one Cl(3), two equivalent Cl(4), and two equivalent Cl(5) atoms. The Rb(1)-Cl(1) bond length is 3.53 Å. The Rb(1)-Cl(2) bond length is 3.42 Å. The Rb(1)-Cl(3) bond length is 3.66 Å. There is one shorter (3.46 Å) and one longer (3.50 Å) Rb(1)-Cl(4) bond length. There is one shorter (3.45 Å) and one longer (3.60 Å) Rb(1)-Cl(5) bond length. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one Cl(2), one Cl(3), one Cl(4), one Cl(5), two equivalent Cl(1), and two equivalent Cl(6) atoms. The Rb(2)-Cl(2) bond length is 3.21 Å. The Rb(2)-Cl(3) bond length is 3.24 Å. The Rb(2)-Cl(4) bond length is 3.43 Å. The Rb(2)-Cl(5) bond length is 3.43 Å. There is one shorter (3.48 Å) and one longer (3.63 Å) Rb(2)-Cl(1) bond length. There is one shorter (3.38 Å) and one longer (3.39 Å) Rb(2)-Cl(6) bond length. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one Cl(1), one Cl(2), one Cl(4), one Cl(5), two equivalent Cl(3), and two equivalent Cl(6) atoms. The Rb(3)-Cl(1) bond length is 3.26 Å. The Rb(3)-Cl(2) bond length is 3.45 Å. The Rb(3)-Cl(4) bond length is 3.25 Å. The Rb(3)-Cl(5) bond length is 3.45 Å. There is one shorter (3.39 Å) and one longer (3.69 Å) Rb(3)-Cl(3) bond length. There is one shorter (3.26 Å) and one longer (3.28 Å) Rb(3)-Cl(6) bond length. There are two inequivalent Tm sites. In the first Tm site, Tm(1) is bonded in an octahedral geometry to two equivalent Cl(2), two equivalent Cl(4), and two equivalent Cl(5) atoms. Both Tm(1)-Cl(2) bond lengths are 2.60 Å. Both Tm(1)-Cl(4) bond lengths are 2.62 Å. Both Tm(1)-Cl(5) bond lengths are 2.57 Å. In the second Tm site, Tm(2) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(3), and two equivalent Cl(6) atoms. Both Tm(2)-Cl(1) bond lengths are 2.61 Å. Both Tm(2)-Cl(3) bond lengths are 2.59 Å. Both Tm(2)-Cl(6) bond lengths are 2.61 Å. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(2), and one Tm(2) atom. In the second Cl site, Cl(2) is bonded in a 4-coordinate geometry to one Rb(1), one Rb(2), one Rb(3), and one Tm(1) atom. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(2), two equivalent Rb(3), and one Tm(2) atom. In the fourth Cl site, Cl(4) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Tm(1) atom to form a mixture of distorted edge, face, and corner-sharing ClRb4Tm square pyramids. In the fifth Cl site, Cl(5) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Tm(1) atom to form a mixture of distorted edge, face, and corner-sharing ClRb4Tm square pyramids. In the sixth Cl site, Cl(6) is bonded in a 5-coordinate geometry to two equivalent Rb(2), two equivalent Rb(3), and one Tm(2) atom.