CsBi3S5 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 8-coordinate geometry to one S(4), two equivalent S(2), two equivalent S(5), and three equivalent S(1) atoms. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 4-55°. In the second Bi site, Bi(2) is bonded to one S(5), two equivalent S(1), and three equivalent S(3) atoms to form a mixture of distorted corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. In the third Bi site, Bi(3) is bonded to one S(3), one S(4), two equivalent S(2), and two equivalent S(5) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 7-55°. There are five inequivalent S sites. In the first S site, S(5) is bonded to two equivalent Cs(1), one Bi(2), and two equivalent Bi(3) atoms to form distorted SCs2Bi3 trigonal bipyramids that share  a cornercorner with one S(3)Bi6 octahedra, corners with two equivalent S(1)Cs3Bi3 octahedra, corners with four equivalent S(4)CsBi3 tetrahedra, corners with four equivalent S(2)Cs2Bi3 trigonal bipyramids, edges with two equivalent S(3)Bi6 octahedra, edges with three equivalent S(1)Cs3Bi3 octahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-21°. In the second S site, S(1) is bonded to three equivalent Cs(1), one Bi(1), and two equivalent Bi(2) atoms to form distorted SCs3Bi3 octahedra that share corners with two equivalent S(3)Bi6 octahedra,  a cornercorner with one S(4)CsBi3 tetrahedra, corners with two equivalent S(5)Cs2Bi3 trigonal bipyramids, corners with five equivalent S(2)Cs2Bi3 trigonal bipyramids, edges with three equivalent S(3)Bi6 octahedra, edges with four equivalent S(1)Cs3Bi3 octahedra, edges with two equivalent S(4)CsBi3 tetrahedra,  an edgeedge with one S(2)Cs2Bi3 trigonal bipyramid, and edges with three equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 7°. In the third S site, S(2) is bonded to two equivalent Cs(1), one Bi(1), and two equivalent Bi(3) atoms to form distorted SCs2Bi3 trigonal bipyramids that share corners with five equivalent S(1)Cs3Bi3 octahedra, corners with two equivalent S(4)CsBi3 tetrahedra, corners with four equivalent S(5)Cs2Bi3 trigonal bipyramids,  an edgeedge with one S(1)Cs3Bi3 octahedra, edges with two equivalent S(3)Bi6 octahedra, edges with two equivalent S(4)CsBi3 tetrahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-50°. In the fourth S site, S(3) is bonded to one Bi(3), two equivalent Bi(1), and three equivalent Bi(2) atoms to form SBi6 octahedra that share corners with two equivalent S(1)Cs3Bi3 octahedra, corners with three equivalent S(4)CsBi3 tetrahedra,  a cornercorner with one S(5)Cs2Bi3 trigonal bipyramid, edges with three equivalent S(1)Cs3Bi3 octahedra, edges with four equivalent S(3)Bi6 octahedra,  an edgeedge with one S(4)CsBi3 tetrahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 7°. In the fifth S site, S(4) is bonded to one Cs(1), one Bi(3), and two equivalent Bi(1) atoms to form distorted SCsBi3 tetrahedra that share  a cornercorner with one S(1)Cs3Bi3 octahedra, corners with three equivalent S(3)Bi6 octahedra, corners with two equivalent S(4)CsBi3 tetrahedra, corners with two equivalent S(2)Cs2Bi3 trigonal bipyramids, corners with four equivalent S(5)Cs2Bi3 trigonal bipyramids,  an edgeedge with one S(3)Bi6 octahedra, edges with two equivalent S(1)Cs3Bi3 octahedra, and edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 7-17°.
CsBi3S5 crystallizes in the orthorhombic Pnma space group. Cs(1) is bonded in a 8-coordinate geometry to one S(4), two equivalent S(2), two equivalent S(5), and three equivalent S(1) atoms. The Cs(1)-S(4) bond length is 3.47 Å. Both Cs(1)-S(2) bond lengths are 3.75 Å. Both Cs(1)-S(5) bond lengths are 3.51 Å. There are two shorter (3.78 Å) and one longer (4.03 Å) Cs(1)-S(1) bond length. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(1), one S(2), two equivalent S(3), and two equivalent S(4) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 4-55°. The Bi(1)-S(1) bond length is 3.14 Å. The Bi(1)-S(2) bond length is 2.67 Å. Both Bi(1)-S(3) bond lengths are 2.99 Å. Both Bi(1)-S(4) bond lengths are 2.70 Å. In the second Bi site, Bi(2) is bonded to one S(5), two equivalent S(1), and three equivalent S(3) atoms to form a mixture of distorted corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 4-7°. The Bi(2)-S(5) bond length is 2.62 Å. Both Bi(2)-S(1) bond lengths are 2.73 Å. There are two shorter (3.03 Å) and one longer (3.17 Å) Bi(2)-S(3) bond length. In the third Bi site, Bi(3) is bonded to one S(3), one S(4), two equivalent S(2), and two equivalent S(5) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles range from 7-55°. The Bi(3)-S(3) bond length is 2.84 Å. The Bi(3)-S(4) bond length is 2.78 Å. Both Bi(3)-S(2) bond lengths are 2.81 Å. Both Bi(3)-S(5) bond lengths are 2.87 Å. There are five inequivalent S sites. In the first S site, S(5) is bonded to two equivalent Cs(1), one Bi(2), and two equivalent Bi(3) atoms to form distorted SCs2Bi3 trigonal bipyramids that share  a cornercorner with one S(3)Bi6 octahedra, corners with two equivalent S(1)Cs3Bi3 octahedra, corners with four equivalent S(4)CsBi3 tetrahedra, corners with four equivalent S(2)Cs2Bi3 trigonal bipyramids, edges with two equivalent S(3)Bi6 octahedra, edges with three equivalent S(1)Cs3Bi3 octahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 12-21°. In the second S site, S(1) is bonded to three equivalent Cs(1), one Bi(1), and two equivalent Bi(2) atoms to form distorted SCs3Bi3 octahedra that share corners with two equivalent S(3)Bi6 octahedra,  a cornercorner with one S(4)CsBi3 tetrahedra, corners with two equivalent S(5)Cs2Bi3 trigonal bipyramids, corners with five equivalent S(2)Cs2Bi3 trigonal bipyramids, edges with three equivalent S(3)Bi6 octahedra, edges with four equivalent S(1)Cs3Bi3 octahedra, edges with two equivalent S(4)CsBi3 tetrahedra,  an edgeedge with one S(2)Cs2Bi3 trigonal bipyramid, and edges with three equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 7°. In the third S site, S(2) is bonded to two equivalent Cs(1), one Bi(1), and two equivalent Bi(3) atoms to form distorted SCs2Bi3 trigonal bipyramids that share corners with five equivalent S(1)Cs3Bi3 octahedra, corners with two equivalent S(4)CsBi3 tetrahedra, corners with four equivalent S(5)Cs2Bi3 trigonal bipyramids,  an edgeedge with one S(1)Cs3Bi3 octahedra, edges with two equivalent S(3)Bi6 octahedra, edges with two equivalent S(4)CsBi3 tetrahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 5-50°. In the fourth S site, S(3) is bonded to one Bi(3), two equivalent Bi(1), and three equivalent Bi(2) atoms to form SBi6 octahedra that share corners with two equivalent S(1)Cs3Bi3 octahedra, corners with three equivalent S(4)CsBi3 tetrahedra,  a cornercorner with one S(5)Cs2Bi3 trigonal bipyramid, edges with three equivalent S(1)Cs3Bi3 octahedra, edges with four equivalent S(3)Bi6 octahedra,  an edgeedge with one S(4)CsBi3 tetrahedra, edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids, and edges with two equivalent S(5)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 7°. In the fifth S site, S(4) is bonded to one Cs(1), one Bi(3), and two equivalent Bi(1) atoms to form distorted SCsBi3 tetrahedra that share  a cornercorner with one S(1)Cs3Bi3 octahedra, corners with three equivalent S(3)Bi6 octahedra, corners with two equivalent S(4)CsBi3 tetrahedra, corners with two equivalent S(2)Cs2Bi3 trigonal bipyramids, corners with four equivalent S(5)Cs2Bi3 trigonal bipyramids,  an edgeedge with one S(3)Bi6 octahedra, edges with two equivalent S(1)Cs3Bi3 octahedra, and edges with two equivalent S(2)Cs2Bi3 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 7-17°.