RbCuCl3 crystallizes in the monoclinic C2 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 10-coordinate geometry to one Cl(2), one Cl(5), two equivalent Cl(6), three equivalent Cl(1), and three equivalent Cl(4) atoms. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one Cl(1), one Cl(6), two equivalent Cl(5), three equivalent Cl(2), and three equivalent Cl(3) atoms. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent Cl(1), two equivalent Cl(4), and two equivalent Cl(6) atoms to form distorted face-sharing CuCl6 octahedra. In the second Cu site, Cu(2) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), and one Cl(6) atom to form distorted face-sharing CuCl6 octahedra. In the third Cu site, Cu(3) is bonded to two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(5) atoms to form distorted face-sharing CuCl6 octahedra. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 1-coordinate geometry to one Rb(2), three equivalent Rb(1), one Cu(1), and one Cu(2) atom. In the second Cl site, Cl(2) is bonded in a 1-coordinate geometry to one Rb(1), three equivalent Rb(2), one Cu(2), and one Cu(3) atom. In the third Cl site, Cl(3) is bonded in a distorted L-shaped geometry to three equivalent Rb(2), one Cu(2), and one Cu(3) atom. In the fourth Cl site, Cl(4) is bonded in a distorted L-shaped geometry to three equivalent Rb(1), one Cu(1), and one Cu(2) atom. In the fifth Cl site, Cl(5) is bonded in a 5-coordinate geometry to one Rb(1), two equivalent Rb(2), one Cu(2), and one Cu(3) atom. In the sixth Cl site, Cl(6) is bonded in a 5-coordinate geometry to one Rb(2), two equivalent Rb(1), one Cu(1), and one Cu(2) atom.
RbCuCl3 crystallizes in the monoclinic C2 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 10-coordinate geometry to one Cl(2), one Cl(5), two equivalent Cl(6), three equivalent Cl(1), and three equivalent Cl(4) atoms. The Rb(1)-Cl(2) bond length is 3.89 Å. The Rb(1)-Cl(5) bond length is 3.37 Å. There is one shorter (3.52 Å) and one longer (3.54 Å) Rb(1)-Cl(6) bond length. There are a spread of Rb(1)-Cl(1) bond distances ranging from 3.46-3.57 Å. There are a spread of Rb(1)-Cl(4) bond distances ranging from 3.53-3.81 Å. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one Cl(1), one Cl(6), two equivalent Cl(5), three equivalent Cl(2), and three equivalent Cl(3) atoms. The Rb(2)-Cl(1) bond length is 3.91 Å. The Rb(2)-Cl(6) bond length is 3.39 Å. There is one shorter (3.51 Å) and one longer (3.56 Å) Rb(2)-Cl(5) bond length. There are a spread of Rb(2)-Cl(2) bond distances ranging from 3.40-3.57 Å. There are a spread of Rb(2)-Cl(3) bond distances ranging from 3.52-3.74 Å. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent Cl(1), two equivalent Cl(4), and two equivalent Cl(6) atoms to form distorted face-sharing CuCl6 octahedra. Both Cu(1)-Cl(1) bond lengths are 2.29 Å. Both Cu(1)-Cl(4) bond lengths are 2.35 Å. Both Cu(1)-Cl(6) bond lengths are 2.87 Å. In the second Cu site, Cu(2) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), and one Cl(6) atom to form distorted face-sharing CuCl6 octahedra. The Cu(2)-Cl(1) bond length is 2.89 Å. The Cu(2)-Cl(2) bond length is 2.90 Å. The Cu(2)-Cl(3) bond length is 2.35 Å. The Cu(2)-Cl(4) bond length is 2.35 Å. The Cu(2)-Cl(5) bond length is 2.30 Å. The Cu(2)-Cl(6) bond length is 2.29 Å. In the third Cu site, Cu(3) is bonded to two equivalent Cl(2), two equivalent Cl(3), and two equivalent Cl(5) atoms to form distorted face-sharing CuCl6 octahedra. Both Cu(3)-Cl(2) bond lengths are 2.30 Å. Both Cu(3)-Cl(3) bond lengths are 2.36 Å. Both Cu(3)-Cl(5) bond lengths are 2.82 Å. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 1-coordinate geometry to one Rb(2), three equivalent Rb(1), one Cu(1), and one Cu(2) atom. In the second Cl site, Cl(2) is bonded in a 1-coordinate geometry to one Rb(1), three equivalent Rb(2), one Cu(2), and one Cu(3) atom. In the third Cl site, Cl(3) is bonded in a distorted L-shaped geometry to three equivalent Rb(2), one Cu(2), and one Cu(3) atom. In the fourth Cl site, Cl(4) is bonded in a distorted L-shaped geometry to three equivalent Rb(1), one Cu(1), and one Cu(2) atom. In the fifth Cl site, Cl(5) is bonded in a 5-coordinate geometry to one Rb(1), two equivalent Rb(2), one Cu(2), and one Cu(3) atom. In the sixth Cl site, Cl(6) is bonded in a 5-coordinate geometry to one Rb(2), two equivalent Rb(1), one Cu(1), and one Cu(2) atom.