Rb3YCl6 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 8-coordinate geometry to one Cl(1), one Cl(3), two equivalent Cl(2), two equivalent Cl(5), and two equivalent Cl(6) atoms. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one Cl(1), one Cl(2), one Cl(5), one Cl(6), two equivalent Cl(3), and two equivalent Cl(4) atoms. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one Cl(2), one Cl(3), one Cl(5), one Cl(6), two equivalent Cl(1), and two equivalent Cl(4) atoms. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded in an octahedral geometry to two equivalent Cl(2), two equivalent Cl(5), and two equivalent Cl(6) atoms. In the second Y site, Y(2) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(3), and two equivalent Cl(4) 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(2), two equivalent Rb(3), and one Y(2) atom. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(3), two equivalent Rb(1), and one Y(1) atom. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(2), and one Y(2) atom. In the fourth Cl site, Cl(4) is bonded in a 5-coordinate geometry to two equivalent Rb(2), two equivalent Rb(3), and one Y(2) atom. In the fifth Cl site, Cl(5) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Y(1) atom to form distorted face-sharing ClRb4Y square pyramids. In the sixth Cl site, Cl(6) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(3), two equivalent Rb(1), and one Y(1) atom.
Rb3YCl6 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 8-coordinate geometry to one Cl(1), one Cl(3), two equivalent Cl(2), two equivalent Cl(5), and two equivalent Cl(6) atoms. The Rb(1)-Cl(1) bond length is 3.48 Å. The Rb(1)-Cl(3) bond length is 3.80 Å. There is one shorter (3.44 Å) and one longer (3.87 Å) Rb(1)-Cl(2) bond length. There is one shorter (3.44 Å) and one longer (3.54 Å) Rb(1)-Cl(5) bond length. There is one shorter (3.44 Å) and one longer (3.73 Å) Rb(1)-Cl(6) bond length. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one Cl(1), one Cl(2), one Cl(5), one Cl(6), two equivalent Cl(3), and two equivalent Cl(4) atoms. The Rb(2)-Cl(1) bond length is 3.26 Å. The Rb(2)-Cl(2) bond length is 3.46 Å. The Rb(2)-Cl(5) bond length is 3.27 Å. The Rb(2)-Cl(6) bond length is 3.48 Å. There is one shorter (3.37 Å) and one longer (3.78 Å) Rb(2)-Cl(3) bond length. There is one shorter (3.28 Å) and one longer (3.29 Å) Rb(2)-Cl(4) bond length. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one Cl(2), one Cl(3), one Cl(5), one Cl(6), two equivalent Cl(1), and two equivalent Cl(4) atoms. The Rb(3)-Cl(2) bond length is 3.20 Å. The Rb(3)-Cl(3) bond length is 3.21 Å. The Rb(3)-Cl(5) bond length is 3.41 Å. The Rb(3)-Cl(6) bond length is 3.44 Å. There is one shorter (3.52 Å) and one longer (3.63 Å) Rb(3)-Cl(1) bond length. There is one shorter (3.38 Å) and one longer (3.40 Å) Rb(3)-Cl(4) bond length. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded in an octahedral geometry to two equivalent Cl(2), two equivalent Cl(5), and two equivalent Cl(6) atoms. Both Y(1)-Cl(2) bond lengths are 2.64 Å. Both Y(1)-Cl(5) bond lengths are 2.65 Å. Both Y(1)-Cl(6) bond lengths are 2.61 Å. In the second Y site, Y(2) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(3), and two equivalent Cl(4) atoms. Both Y(2)-Cl(1) bond lengths are 2.66 Å. Both Y(2)-Cl(3) bond lengths are 2.62 Å. Both Y(2)-Cl(4) bond lengths are 2.66 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(2), two equivalent Rb(3), and one Y(2) atom. In the second Cl site, Cl(2) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(3), two equivalent Rb(1), and one Y(1) atom. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), two equivalent Rb(2), and one Y(2) atom. In the fourth Cl site, Cl(4) is bonded in a 5-coordinate geometry to two equivalent Rb(2), two equivalent Rb(3), and one Y(2) atom. In the fifth Cl site, Cl(5) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Y(1) atom to form distorted face-sharing ClRb4Y square pyramids. In the sixth Cl site, Cl(6) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(3), two equivalent Rb(1), and one Y(1) atom.