RbCrI3 crystallizes in the monoclinic C2 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one I(2), two equivalent I(1), three equivalent I(4), and three equivalent I(6) atoms. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one I(1), two equivalent I(2), three equivalent I(3), and three equivalent I(5) atoms. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one I(1), one I(2), one I(3), one I(4), one I(5), and one I(6) atom to form face-sharing CrI6 octahedra. In the second Cr site, Cr(2) is bonded to two equivalent I(2), two equivalent I(3), and two equivalent I(5) atoms to form face-sharing CrI6 octahedra. In the third Cr site, Cr(3) is bonded to two equivalent I(1), two equivalent I(4), and two equivalent I(6) atoms to form face-sharing CrI6 octahedra. There are six inequivalent I sites. In the first I site, I(1) is bonded in a 5-coordinate geometry to one Rb(2), two equivalent Rb(1), one Cr(1), and one Cr(3) atom. In the second I site, I(2) is bonded in a 5-coordinate geometry to one Rb(1), two equivalent Rb(2), one Cr(1), and one Cr(2) atom. In the third I site, I(3) is bonded in a 5-coordinate geometry to three equivalent Rb(2), one Cr(1), and one Cr(2) atom. In the fourth I site, I(4) is bonded to three equivalent Rb(1), one Cr(1), and one Cr(3) atom to form a mixture of distorted edge, face, and corner-sharing IRb3Cr2 square pyramids. In the fifth I site, I(5) is bonded to three equivalent Rb(2), one Cr(1), and one Cr(2) atom to form a mixture of distorted face and corner-sharing IRb3Cr2 square pyramids. In the sixth I site, I(6) is bonded to three equivalent Rb(1), one Cr(1), and one Cr(3) atom to form a mixture of distorted edge, face, and corner-sharing IRb3Cr2 square pyramids.
RbCrI3 crystallizes in the monoclinic C2 space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one I(2), two equivalent I(1), three equivalent I(4), and three equivalent I(6) atoms. The Rb(1)-I(2) bond length is 3.73 Å. There is one shorter (4.05 Å) and one longer (4.18 Å) Rb(1)-I(1) bond length. There are a spread of Rb(1)-I(4) bond distances ranging from 4.01-4.10 Å. There are a spread of Rb(1)-I(6) bond distances ranging from 3.84-4.12 Å. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one I(1), two equivalent I(2), three equivalent I(3), and three equivalent I(5) atoms. The Rb(2)-I(1) bond length is 3.74 Å. There is one shorter (4.09 Å) and one longer (4.13 Å) Rb(2)-I(2) bond length. There are a spread of Rb(2)-I(3) bond distances ranging from 3.82-4.15 Å. There are a spread of Rb(2)-I(5) bond distances ranging from 4.02-4.12 Å. There are three inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one I(1), one I(2), one I(3), one I(4), one I(5), and one I(6) atom to form face-sharing CrI6 octahedra. The Cr(1)-I(1) bond length is 2.77 Å. The Cr(1)-I(2) bond length is 2.77 Å. The Cr(1)-I(3) bond length is 3.20 Å. The Cr(1)-I(4) bond length is 2.79 Å. The Cr(1)-I(5) bond length is 2.79 Å. The Cr(1)-I(6) bond length is 3.20 Å. In the second Cr site, Cr(2) is bonded to two equivalent I(2), two equivalent I(3), and two equivalent I(5) atoms to form face-sharing CrI6 octahedra. Both Cr(2)-I(2) bond lengths are 3.15 Å. Both Cr(2)-I(3) bond lengths are 2.77 Å. Both Cr(2)-I(5) bond lengths are 2.80 Å. In the third Cr site, Cr(3) is bonded to two equivalent I(1), two equivalent I(4), and two equivalent I(6) atoms to form face-sharing CrI6 octahedra. Both Cr(3)-I(1) bond lengths are 3.15 Å. Both Cr(3)-I(4) bond lengths are 2.80 Å. Both Cr(3)-I(6) bond lengths are 2.77 Å. There are six inequivalent I sites. In the first I site, I(1) is bonded in a 5-coordinate geometry to one Rb(2), two equivalent Rb(1), one Cr(1), and one Cr(3) atom. In the second I site, I(2) is bonded in a 5-coordinate geometry to one Rb(1), two equivalent Rb(2), one Cr(1), and one Cr(2) atom. In the third I site, I(3) is bonded in a 5-coordinate geometry to three equivalent Rb(2), one Cr(1), and one Cr(2) atom. In the fourth I site, I(4) is bonded to three equivalent Rb(1), one Cr(1), and one Cr(3) atom to form a mixture of distorted edge, face, and corner-sharing IRb3Cr2 square pyramids. In the fifth I site, I(5) is bonded to three equivalent Rb(2), one Cr(1), and one Cr(2) atom to form a mixture of distorted face and corner-sharing IRb3Cr2 square pyramids. In the sixth I site, I(6) is bonded to three equivalent Rb(1), one Cr(1), and one Cr(3) atom to form a mixture of distorted edge, face, and corner-sharing IRb3Cr2 square pyramids.