Rb3TbCl6 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 Tb sites. In the first Tb site, Tb(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 Tb site, Tb(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 Tb(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 Tb(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 Tb(2) atom. In the fourth Cl site, Cl(4) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Tb(1) atom to form a mixture of distorted corner, face, and edge-sharing ClRb4Tb square pyramids. In the fifth Cl site, Cl(5) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Tb(1) atom to form a mixture of distorted corner, face, and edge-sharing ClRb4Tb 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 Tb(2) atom.
Rb3TbCl6 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 3.52 Å. The Rb(1)-Cl(2) bond length is 3.40 Å. The Rb(1)-Cl(3) bond length is 3.65 Å. There is one shorter (3.42 Å) and one longer (3.55 Å) Rb(1)-Cl(4) bond length. There is one shorter (3.45 Å) and one longer (3.64 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 3.25 Å. The Rb(2)-Cl(4) bond length is 3.40 Å. The Rb(2)-Cl(5) bond length is 3.44 Å. There is one shorter (3.49 Å) and one longer (3.67 Å) Rb(2)-Cl(1) bond length. Both Rb(2)-Cl(6) bond lengths are 3.40 Å. 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 3.27 Å. The Rb(3)-Cl(2) bond length is 3.43 Å. The Rb(3)-Cl(4) bond length is 3.26 Å. The Rb(3)-Cl(5) bond length is 3.48 Å. There is one shorter (3.41 Å) and one longer (3.72 Å) Rb(3)-Cl(3) bond length. There is one shorter (3.27 Å) and one longer (3.29 Å) Rb(3)-Cl(6) bond length. There are two inequivalent Tb sites. In the first Tb site, Tb(1) is bonded in an octahedral geometry to two equivalent Cl(2), two equivalent Cl(4), and two equivalent Cl(5) atoms. Both Tb(1)-Cl(2) bond lengths are 2.64 Å. Both Tb(1)-Cl(4) bond lengths are 2.67 Å. Both Tb(1)-Cl(5) bond lengths are 2.63 Å. In the second Tb site, Tb(2) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(3), and two equivalent Cl(6) atoms. Both Tb(2)-Cl(1) bond lengths are 2.66 Å. Both Tb(2)-Cl(3) bond lengths are 2.64 Å. Both Tb(2)-Cl(6) bond lengths are 2.67 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 Tb(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 Tb(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 Tb(2) atom. In the fourth Cl site, Cl(4) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Tb(1) atom to form a mixture of distorted corner, face, and edge-sharing ClRb4Tb square pyramids. In the fifth Cl site, Cl(5) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Tb(1) atom to form a mixture of distorted corner, face, and edge-sharing ClRb4Tb 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 Tb(2) atom.