CsIn5S8 is Orthorhombic Perovskite-like structured and crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 10-coordinate geometry to two equivalent S(3), four equivalent S(1), and four equivalent S(2) atoms. There are three inequivalent In sites. In the first In site, In(1) is bonded to two equivalent S(2) and four equivalent S(3) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the second In site, In(2) is bonded to one S(3), two equivalent S(2), and three equivalent S(4) atoms to form a mixture of distorted face, corner, and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. In the third In site, In(3) is bonded to one S(3), two equivalent S(4), and three equivalent S(1) atoms to form a mixture of face, corner, and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1) and three equivalent In(3) atoms. In the second S site, S(2) is bonded to two equivalent Cs(1), one In(1), and two equivalent In(2) atoms to form distorted SCs2In3 trigonal bipyramids that share corners with three equivalent S(2)Cs2In3 trigonal bipyramids, corners with two equivalent S(3)CsIn4 trigonal pyramids, edges with three equivalent S(2)Cs2In3 trigonal bipyramids, and edges with four equivalent S(3)CsIn4 trigonal pyramids. In the third S site, S(3) is bonded to one Cs(1), one In(2), one In(3), and two equivalent In(1) atoms to form distorted SCsIn4 trigonal pyramids that share corners with two equivalent S(2)Cs2In3 trigonal bipyramids, corners with five equivalent S(3)CsIn4 trigonal pyramids, edges with four equivalent S(2)Cs2In3 trigonal bipyramids, and  an edgeedge with one S(3)CsIn4 trigonal pyramid. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent In(3) and three equivalent In(2) atoms.
CsIn5S8 is Orthorhombic Perovskite-like structured and crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 10-coordinate geometry to two equivalent S(3), four equivalent S(1), and four equivalent S(2) atoms. Both Cs(1)-S(3) bond lengths are 4.03 Å. All Cs(1)-S(1) bond lengths are 3.78 Å. All Cs(1)-S(2) bond lengths are 3.53 Å. There are three inequivalent In sites. In the first In site, In(1) is bonded to two equivalent S(2) and four equivalent S(3) atoms to form a mixture of corner and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles are 47°. Both In(1)-S(2) bond lengths are 2.60 Å. All In(1)-S(3) bond lengths are 2.66 Å. In the second In site, In(2) is bonded to one S(3), two equivalent S(2), and three equivalent S(4) atoms to form a mixture of distorted face, corner, and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. The In(2)-S(3) bond length is 2.55 Å. Both In(2)-S(2) bond lengths are 2.54 Å. There is one shorter (2.48 Å) and two longer (3.04 Å) In(2)-S(4) bond lengths. In the third In site, In(3) is bonded to one S(3), two equivalent S(4), and three equivalent S(1) atoms to form a mixture of face, corner, and edge-sharing InS6 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. The In(3)-S(3) bond length is 2.77 Å. Both In(3)-S(4) bond lengths are 2.74 Å. All In(3)-S(1) bond lengths are 2.59 Å. There are four inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Cs(1) and three equivalent In(3) atoms. In the second S site, S(2) is bonded to two equivalent Cs(1), one In(1), and two equivalent In(2) atoms to form distorted SCs2In3 trigonal bipyramids that share corners with three equivalent S(2)Cs2In3 trigonal bipyramids, corners with two equivalent S(3)CsIn4 trigonal pyramids, edges with three equivalent S(2)Cs2In3 trigonal bipyramids, and edges with four equivalent S(3)CsIn4 trigonal pyramids. In the third S site, S(3) is bonded to one Cs(1), one In(2), one In(3), and two equivalent In(1) atoms to form distorted SCsIn4 trigonal pyramids that share corners with two equivalent S(2)Cs2In3 trigonal bipyramids, corners with five equivalent S(3)CsIn4 trigonal pyramids, edges with four equivalent S(2)Cs2In3 trigonal bipyramids, and  an edgeedge with one S(3)CsIn4 trigonal pyramid. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to two equivalent In(3) and three equivalent In(2) atoms.