Rb3Bi2I9 crystallizes in the monoclinic C2/c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to two equivalent I(2), two equivalent I(3), two equivalent I(4), and two equivalent I(5) atoms. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to one I(2), one I(4), two equivalent I(1), and two equivalent I(3) atoms. Bi(1) is bonded to one I(1), one I(3), one I(4), one I(5), and two equivalent I(2) atoms to form face-sharing BiI6 octahedra. There are five inequivalent I sites. In the first I site, I(5) is bonded in a distorted see-saw-like geometry to two equivalent Rb(1) and two equivalent Bi(1) atoms. In the second I site, I(1) is bonded in a 3-coordinate geometry to two equivalent Rb(2) and one Bi(1) atom. In the third I site, I(2) is bonded in a rectangular see-saw-like geometry to one Rb(1), one Rb(2), and two equivalent Bi(1) atoms. In the fourth I site, I(3) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), two equivalent Rb(2), and one Bi(1) atom. In the fifth I site, I(4) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one Rb(2), and one Bi(1) atom.
Rb3Bi2I9 crystallizes in the monoclinic C2/c space group. There are two inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to two equivalent I(2), two equivalent I(3), two equivalent I(4), and two equivalent I(5) atoms. Both Rb(1)-I(2) bond lengths are 3.92 Å. Both Rb(1)-I(3) bond lengths are 4.11 Å. Both Rb(1)-I(4) bond lengths are 3.76 Å. Both Rb(1)-I(5) bond lengths are 4.22 Å. In the second Rb site, Rb(2) is bonded in a 6-coordinate geometry to one I(2), one I(4), two equivalent I(1), and two equivalent I(3) atoms. The Rb(2)-I(2) bond length is 3.84 Å. The Rb(2)-I(4) bond length is 3.87 Å. There is one shorter (3.69 Å) and one longer (4.15 Å) Rb(2)-I(1) bond length. There is one shorter (3.80 Å) and one longer (4.12 Å) Rb(2)-I(3) bond length. Bi(1) is bonded to one I(1), one I(3), one I(4), one I(5), and two equivalent I(2) atoms to form face-sharing BiI6 octahedra. The Bi(1)-I(1) bond length is 2.95 Å. The Bi(1)-I(3) bond length is 2.98 Å. The Bi(1)-I(4) bond length is 2.99 Å. The Bi(1)-I(5) bond length is 3.24 Å. There is one shorter (3.21 Å) and one longer (3.28 Å) Bi(1)-I(2) bond length. There are five inequivalent I sites. In the first I site, I(5) is bonded in a distorted see-saw-like geometry to two equivalent Rb(1) and two equivalent Bi(1) atoms. In the second I site, I(1) is bonded in a 3-coordinate geometry to two equivalent Rb(2) and one Bi(1) atom. In the third I site, I(2) is bonded in a rectangular see-saw-like geometry to one Rb(1), one Rb(2), and two equivalent Bi(1) atoms. In the fourth I site, I(3) is bonded in a distorted rectangular see-saw-like geometry to one Rb(1), two equivalent Rb(2), and one Bi(1) atom. In the fifth I site, I(4) is bonded in a distorted trigonal non-coplanar geometry to one Rb(1), one Rb(2), and one Bi(1) atom.