Rb2InOCl5 crystallizes in the orthorhombic Pnma space group. Rb(1) is bonded in a 11-coordinate geometry to one O(1), two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(3), and four equivalent Cl(4) atoms. In(1) is bonded to one O(1), one Cl(1), one Cl(2), one Cl(3), and two equivalent Cl(4) atoms to form distorted InCl5O octahedra that share  a cornercorner with one Cl(1)Rb4InO octahedra. The corner-sharing octahedral tilt angles are 108°. O(1) is bonded in a distorted single-bond geometry to two equivalent Rb(1), one In(1), and one Cl(1) atom. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Rb(1), one In(1), and one O(1) atom to form distorted ClRb4InO octahedra that share  a cornercorner with one In(1)Cl5O octahedra, corners with four equivalent Cl(1)Rb4InO octahedra, corners with five equivalent Cl(3)Rb4In square pyramids, edges with two equivalent Cl(3)Rb4In square pyramids, edges with three equivalent Cl(2)Rb4In square pyramids, and  a faceface with one Cl(2)Rb4In square pyramid. The corner-sharing octahedral tilt angles range from 53-108°. In the second Cl site, Cl(2) is bonded to four equivalent Rb(1) and one In(1) atom to form distorted ClRb4In square pyramids that share corners with four equivalent Cl(2)Rb4In square pyramids, corners with four equivalent Cl(3)Rb4In square pyramids, edges with three equivalent Cl(1)Rb4InO octahedra,  an edgeedge with one Cl(3)Rb4In square pyramid,  a faceface with one Cl(1)Rb4InO octahedra, and  a faceface with one Cl(3)Rb4In square pyramid. In the third Cl site, Cl(3) is bonded to four equivalent Rb(1) and one In(1) atom to form distorted ClRb4In square pyramids that share corners with five equivalent Cl(1)Rb4InO octahedra, corners with four equivalent Cl(2)Rb4In square pyramids, edges with two equivalent Cl(1)Rb4InO octahedra,  an edgeedge with one Cl(2)Rb4In square pyramid, edges with two equivalent Cl(3)Rb4In square pyramids, and  a faceface with one Cl(2)Rb4In square pyramid. The corner-sharing octahedral tilt angles range from 9-60°. In the fourth Cl site, Cl(4) is bonded in a 5-coordinate geometry to four equivalent Rb(1) and one In(1) atom.
Rb2InOCl5 crystallizes in the orthorhombic Pnma space group. Rb(1) is bonded in a 11-coordinate geometry to one O(1), two equivalent Cl(1), two equivalent Cl(2), two equivalent Cl(3), and four equivalent Cl(4) atoms. The Rb(1)-O(1) bond length is 3.22 Å. There is one shorter (3.39 Å) and one longer (3.69 Å) Rb(1)-Cl(1) bond length. There is one shorter (3.52 Å) and one longer (3.58 Å) Rb(1)-Cl(2) bond length. There is one shorter (3.42 Å) and one longer (3.57 Å) Rb(1)-Cl(3) bond length. There are a spread of Rb(1)-Cl(4) bond distances ranging from 3.46-3.76 Å. In(1) is bonded to one O(1), one Cl(1), one Cl(2), one Cl(3), and two equivalent Cl(4) atoms to form distorted InCl5O octahedra that share  a cornercorner with one Cl(1)Rb4InO octahedra. The corner-sharing octahedral tilt angles are 108°. The In(1)-O(1) bond length is 2.21 Å. The In(1)-Cl(1) bond length is 2.71 Å. The In(1)-Cl(2) bond length is 2.44 Å. The In(1)-Cl(3) bond length is 2.47 Å. Both In(1)-Cl(4) bond lengths are 2.48 Å. O(1) is bonded in a distorted single-bond geometry to two equivalent Rb(1), one In(1), and one Cl(1) atom. The O(1)-Cl(1) bond length is 2.40 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to four equivalent Rb(1), one In(1), and one O(1) atom to form distorted ClRb4InO octahedra that share  a cornercorner with one In(1)Cl5O octahedra, corners with four equivalent Cl(1)Rb4InO octahedra, corners with five equivalent Cl(3)Rb4In square pyramids, edges with two equivalent Cl(3)Rb4In square pyramids, edges with three equivalent Cl(2)Rb4In square pyramids, and  a faceface with one Cl(2)Rb4In square pyramid. The corner-sharing octahedral tilt angles range from 53-108°. In the second Cl site, Cl(2) is bonded to four equivalent Rb(1) and one In(1) atom to form distorted ClRb4In square pyramids that share corners with four equivalent Cl(2)Rb4In square pyramids, corners with four equivalent Cl(3)Rb4In square pyramids, edges with three equivalent Cl(1)Rb4InO octahedra,  an edgeedge with one Cl(3)Rb4In square pyramid,  a faceface with one Cl(1)Rb4InO octahedra, and  a faceface with one Cl(3)Rb4In square pyramid. In the third Cl site, Cl(3) is bonded to four equivalent Rb(1) and one In(1) atom to form distorted ClRb4In square pyramids that share corners with five equivalent Cl(1)Rb4InO octahedra, corners with four equivalent Cl(2)Rb4In square pyramids, edges with two equivalent Cl(1)Rb4InO octahedra,  an edgeedge with one Cl(2)Rb4In square pyramid, edges with two equivalent Cl(3)Rb4In square pyramids, and  a faceface with one Cl(2)Rb4In square pyramid. The corner-sharing octahedral tilt angles range from 9-60°. In the fourth Cl site, Cl(4) is bonded in a 5-coordinate geometry to four equivalent Rb(1) and one In(1) atom.