Rb3EuCl6 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(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 Eu sites. In the first Eu site, Eu(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 Eu site, Eu(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 to one Rb(1), one Rb(3), two equivalent Rb(2), and one Eu(2) atom to form a mixture of distorted corner and edge-sharing ClRb4Eu trigonal bipyramids. 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 Eu(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 Eu(2) atom. In the fourth Cl site, Cl(4) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Eu(1) atom to form a mixture of distorted corner, edge, and face-sharing ClRb4Eu square pyramids. In the fifth Cl site, Cl(5) is bonded in a 1-coordinate geometry to one Rb(2), one Rb(3), two equivalent Rb(1), and one Eu(1) atom. 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 Eu(2) atom.
Rb3EuCl6 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(4), and two equivalent Cl(5) atoms. The Rb(1)-Cl(1) bond length is 3.61 Å. The Rb(1)-Cl(3) bond length is 3.78 Å. There is one shorter (3.55 Å) and one longer (3.85 Å) Rb(1)-Cl(2) bond length. There is one shorter (3.57 Å) and one longer (3.62 Å) Rb(1)-Cl(4) bond length. There is one shorter (3.59 Å) and one longer (3.87 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 3.24 Å. The Rb(2)-Cl(3) bond length is 3.29 Å. The Rb(2)-Cl(4) bond length is 3.52 Å. The Rb(2)-Cl(5) bond length is 3.45 Å. There is one shorter (3.62 Å) and one longer (3.70 Å) Rb(2)-Cl(1) bond length. There is one shorter (3.44 Å) and one longer (3.49 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 3.31 Å. The Rb(3)-Cl(2) bond length is 3.60 Å. The Rb(3)-Cl(4) bond length is 3.34 Å. The Rb(3)-Cl(5) bond length is 3.53 Å. There is one shorter (3.55 Å) and one longer (3.74 Å) Rb(3)-Cl(3) bond length. There is one shorter (3.34 Å) and one longer (3.37 Å) Rb(3)-Cl(6) bond length. There are two inequivalent Eu sites. In the first Eu site, Eu(1) is bonded in an octahedral geometry to two equivalent Cl(2), two equivalent Cl(4), and two equivalent Cl(5) atoms. Both Eu(1)-Cl(2) bond lengths are 2.73 Å. Both Eu(1)-Cl(4) bond lengths are 2.75 Å. Both Eu(1)-Cl(5) bond lengths are 2.71 Å. In the second Eu site, Eu(2) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(3), and two equivalent Cl(6) atoms. Both Eu(2)-Cl(1) bond lengths are 2.76 Å. Both Eu(2)-Cl(3) bond lengths are 2.73 Å. Both Eu(2)-Cl(6) bond lengths are 2.76 Å. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Rb(1), one Rb(3), two equivalent Rb(2), and one Eu(2) atom to form a mixture of distorted corner and edge-sharing ClRb4Eu trigonal bipyramids. 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 Eu(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 Eu(2) atom. In the fourth Cl site, Cl(4) is bonded to one Rb(2), one Rb(3), two equivalent Rb(1), and one Eu(1) atom to form a mixture of distorted corner, edge, and face-sharing ClRb4Eu square pyramids. In the fifth Cl site, Cl(5) is bonded in a 1-coordinate geometry to one Rb(2), one Rb(3), two equivalent Rb(1), and one Eu(1) atom. 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 Eu(2) atom.