Cs5U2S4ICl8 crystallizes in the orthorhombic Immm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent S(1), one I(1), three equivalent Cl(2), and four equivalent Cl(1) atoms. In the second Cs site, Cs(2) is bonded to two equivalent I(1) and four equivalent Cl(2) atoms to form corner-sharing CsI2Cl4 octahedra. The corner-sharing octahedra are not tilted. U(1) is bonded in a 8-coordinate geometry to four equivalent S(1), two equivalent Cl(1), and two equivalent Cl(2) atoms. S(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent U(1), and one S(1) atom. I(1) is bonded to two equivalent Cs(2) and four equivalent Cs(1) atoms to form ICs6 octahedra that share corners with two equivalent I(1)Cs6 octahedra, corners with four equivalent Cl(2)Cs4U trigonal bipyramids, and edges with eight equivalent Cl(2)Cs4U trigonal bipyramids. The corner-sharing octahedra are not tilted. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to four equivalent Cs(1) and one U(1) atom. In the second Cl site, Cl(2) is bonded to one Cs(2), three equivalent Cs(1), and one U(1) atom to form distorted ClCs4U trigonal bipyramids that share  a cornercorner with one I(1)Cs6 octahedra, corners with six equivalent Cl(2)Cs4U trigonal bipyramids, edges with two equivalent I(1)Cs6 octahedra, and edges with two equivalent Cl(2)Cs4U trigonal bipyramids. The corner-sharing octahedral tilt angles are 40°.
Cs5U2S4ICl8 crystallizes in the orthorhombic Immm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent S(1), one I(1), three equivalent Cl(2), and four equivalent Cl(1) atoms. Both Cs(1)-S(1) bond lengths are 3.97 Å. The Cs(1)-I(1) bond length is 3.87 Å. There is one shorter (3.51 Å) and two longer (3.90 Å) Cs(1)-Cl(2) bond lengths. There are two shorter (3.59 Å) and two longer (3.81 Å) Cs(1)-Cl(1) bond lengths. In the second Cs site, Cs(2) is bonded to two equivalent I(1) and four equivalent Cl(2) atoms to form corner-sharing CsI2Cl4 octahedra. The corner-sharing octahedra are not tilted. Both Cs(2)-I(1) bond lengths are 3.87 Å. All Cs(2)-Cl(2) bond lengths are 3.61 Å. U(1) is bonded in a 8-coordinate geometry to four equivalent S(1), two equivalent Cl(1), and two equivalent Cl(2) atoms. All U(1)-S(1) bond lengths are 2.80 Å. Both U(1)-Cl(1) bond lengths are 2.68 Å. Both U(1)-Cl(2) bond lengths are 2.78 Å. S(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1), two equivalent U(1), and one S(1) atom. The S(1)-S(1) bond length is 2.07 Å. I(1) is bonded to two equivalent Cs(2) and four equivalent Cs(1) atoms to form ICs6 octahedra that share corners with two equivalent I(1)Cs6 octahedra, corners with four equivalent Cl(2)Cs4U trigonal bipyramids, and edges with eight equivalent Cl(2)Cs4U trigonal bipyramids. The corner-sharing octahedra are not tilted. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to four equivalent Cs(1) and one U(1) atom. In the second Cl site, Cl(2) is bonded to one Cs(2), three equivalent Cs(1), and one U(1) atom to form distorted ClCs4U trigonal bipyramids that share  a cornercorner with one I(1)Cs6 octahedra, corners with six equivalent Cl(2)Cs4U trigonal bipyramids, edges with two equivalent I(1)Cs6 octahedra, and edges with two equivalent Cl(2)Cs4U trigonal bipyramids. The corner-sharing octahedral tilt angles are 40°.