Cs2Bi2MnS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(4), and three equivalent S(5) atoms. In the second Cs site, Cs(2) is bonded to one S(1), two equivalent S(3), and three equivalent S(2) atoms to form distorted CsS6 octahedra that share corners with three equivalent Bi(2)S6 octahedra, corners with four equivalent Bi(1)S5 square pyramids, corners with three equivalent Mn(1)S4 tetrahedra, edges with two equivalent Bi(2)S6 octahedra, edges with four equivalent Cs(2)S6 octahedra,  an edgeedge with one Bi(1)S5 square pyramid, and  an edgeedge with one Mn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-59°. Mn(1) is bonded to one S(1), one S(5), and two equivalent S(3) atoms to form MnS4 tetrahedra that share corners with three equivalent Cs(2)S6 octahedra, corners with two equivalent Bi(1)S5 square pyramids, corners with two equivalent Mn(1)S4 tetrahedra,  an edgeedge with one Cs(2)S6 octahedra, and edges with two equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-27°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(4), two equivalent S(2), and two equivalent S(5) atoms to form distorted BiS5 square pyramids that share corners with four equivalent Cs(2)S6 octahedra, corners with two equivalent Mn(1)S4 tetrahedra,  an edgeedge with one Cs(2)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, and edges with two equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 11-89°. In the second Bi site, Bi(2) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(4) atoms to form BiS6 octahedra that share corners with three equivalent Cs(2)S6 octahedra, edges with two equivalent Cs(2)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, edges with two equivalent Bi(1)S5 square pyramids, and edges with two equivalent Mn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-59°. There are five inequivalent S sites. In the first S site, S(1) is bonded to one Cs(2), two equivalent Cs(1), one Mn(1), and two equivalent Bi(2) atoms to form distorted SCs3MnBi2 octahedra that share  a cornercorner with one S(2)Cs3Bi3 octahedra, corners with four equivalent S(5)Cs3MnBi2 octahedra, corners with four equivalent S(4)Cs2Bi3 square pyramids, edges with two equivalent S(2)Cs3Bi3 octahedra, edges with two equivalent S(1)Cs3MnBi2 octahedra, edges with two equivalent S(4)Cs2Bi3 square pyramids, and  a faceface with one S(5)Cs3MnBi2 octahedra. The corner-sharing octahedral tilt angles range from 16-73°. In the second S site, S(2) is bonded to three equivalent Cs(2), one Bi(2), and two equivalent Bi(1) atoms to form SCs3Bi3 octahedra that share  a cornercorner with one S(1)Cs3MnBi2 octahedra, corners with two equivalent S(5)Cs3MnBi2 octahedra,  an edgeedge with one S(5)Cs3MnBi2 octahedra, edges with two equivalent S(1)Cs3MnBi2 octahedra, edges with four equivalent S(2)Cs3Bi3 octahedra, and edges with two equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 2-16°. In the third S site, S(3) is bonded in a 2-coordinate geometry to two equivalent Cs(2), two equivalent Mn(1), and one Bi(2) atom. In the fourth S site, S(4) is bonded to two equivalent Cs(1), one Bi(1), and two equivalent Bi(2) atoms to form SCs2Bi3 square pyramids that share corners with two equivalent S(5)Cs3MnBi2 octahedra, corners with four equivalent S(1)Cs3MnBi2 octahedra, edges with two equivalent S(2)Cs3Bi3 octahedra, edges with two equivalent S(1)Cs3MnBi2 octahedra, edges with three equivalent S(5)Cs3MnBi2 octahedra, and edges with two equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 4-47°. In the fifth S site, S(5) is bonded to three equivalent Cs(1), one Mn(1), and two equivalent Bi(1) atoms to form distorted SCs3MnBi2 octahedra that share corners with two equivalent S(2)Cs3Bi3 octahedra, corners with four equivalent S(1)Cs3MnBi2 octahedra, corners with two equivalent S(4)Cs2Bi3 square pyramids,  an edgeedge with one S(2)Cs3Bi3 octahedra, edges with four equivalent S(5)Cs3MnBi2 octahedra, edges with three equivalent S(4)Cs2Bi3 square pyramids, and  a faceface with one S(1)Cs3MnBi2 octahedra. The corner-sharing octahedral tilt angles range from 2-73°.
Cs2Bi2MnS5 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 7-coordinate geometry to two equivalent S(1), two equivalent S(4), and three equivalent S(5) atoms. Both Cs(1)-S(1) bond lengths are 3.57 Å. Both Cs(1)-S(4) bond lengths are 3.54 Å. There is one shorter (3.55 Å) and two longer (3.62 Å) Cs(1)-S(5) bond lengths. In the second Cs site, Cs(2) is bonded to one S(1), two equivalent S(3), and three equivalent S(2) atoms to form distorted CsS6 octahedra that share corners with three equivalent Bi(2)S6 octahedra, corners with four equivalent Bi(1)S5 square pyramids, corners with three equivalent Mn(1)S4 tetrahedra, edges with two equivalent Bi(2)S6 octahedra, edges with four equivalent Cs(2)S6 octahedra,  an edgeedge with one Bi(1)S5 square pyramid, and  an edgeedge with one Mn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-59°. The Cs(2)-S(1) bond length is 3.48 Å. Both Cs(2)-S(3) bond lengths are 3.58 Å. There are two shorter (3.63 Å) and one longer (3.65 Å) Cs(2)-S(2) bond length. Mn(1) is bonded to one S(1), one S(5), and two equivalent S(3) atoms to form MnS4 tetrahedra that share corners with three equivalent Cs(2)S6 octahedra, corners with two equivalent Bi(1)S5 square pyramids, corners with two equivalent Mn(1)S4 tetrahedra,  an edgeedge with one Cs(2)S6 octahedra, and edges with two equivalent Bi(2)S6 octahedra. The corner-sharing octahedral tilt angles range from 1-27°. The Mn(1)-S(1) bond length is 2.42 Å. The Mn(1)-S(5) bond length is 2.40 Å. Both Mn(1)-S(3) bond lengths are 2.46 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one S(4), two equivalent S(2), and two equivalent S(5) atoms to form distorted BiS5 square pyramids that share corners with four equivalent Cs(2)S6 octahedra, corners with two equivalent Mn(1)S4 tetrahedra,  an edgeedge with one Cs(2)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, and edges with two equivalent Bi(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 11-89°. The Bi(1)-S(4) bond length is 2.66 Å. Both Bi(1)-S(2) bond lengths are 2.92 Å. Both Bi(1)-S(5) bond lengths are 2.83 Å. In the second Bi site, Bi(2) is bonded to one S(2), one S(3), two equivalent S(1), and two equivalent S(4) atoms to form BiS6 octahedra that share corners with three equivalent Cs(2)S6 octahedra, edges with two equivalent Cs(2)S6 octahedra, edges with two equivalent Bi(2)S6 octahedra, edges with two equivalent Bi(1)S5 square pyramids, and edges with two equivalent Mn(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-59°. The Bi(2)-S(2) bond length is 2.78 Å. The Bi(2)-S(3) bond length is 2.98 Å. Both Bi(2)-S(1) bond lengths are 2.85 Å. Both Bi(2)-S(4) bond lengths are 2.87 Å. There are five inequivalent S sites. In the first S site, S(1) is bonded to one Cs(2), two equivalent Cs(1), one Mn(1), and two equivalent Bi(2) atoms to form distorted SCs3MnBi2 octahedra that share  a cornercorner with one S(2)Cs3Bi3 octahedra, corners with four equivalent S(5)Cs3MnBi2 octahedra, corners with four equivalent S(4)Cs2Bi3 square pyramids, edges with two equivalent S(2)Cs3Bi3 octahedra, edges with two equivalent S(1)Cs3MnBi2 octahedra, edges with two equivalent S(4)Cs2Bi3 square pyramids, and  a faceface with one S(5)Cs3MnBi2 octahedra. The corner-sharing octahedral tilt angles range from 16-73°. In the second S site, S(2) is bonded to three equivalent Cs(2), one Bi(2), and two equivalent Bi(1) atoms to form SCs3Bi3 octahedra that share  a cornercorner with one S(1)Cs3MnBi2 octahedra, corners with two equivalent S(5)Cs3MnBi2 octahedra,  an edgeedge with one S(5)Cs3MnBi2 octahedra, edges with two equivalent S(1)Cs3MnBi2 octahedra, edges with four equivalent S(2)Cs3Bi3 octahedra, and edges with two equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 2-16°. In the third S site, S(3) is bonded in a 2-coordinate geometry to two equivalent Cs(2), two equivalent Mn(1), and one Bi(2) atom. In the fourth S site, S(4) is bonded to two equivalent Cs(1), one Bi(1), and two equivalent Bi(2) atoms to form SCs2Bi3 square pyramids that share corners with two equivalent S(5)Cs3MnBi2 octahedra, corners with four equivalent S(1)Cs3MnBi2 octahedra, edges with two equivalent S(2)Cs3Bi3 octahedra, edges with two equivalent S(1)Cs3MnBi2 octahedra, edges with three equivalent S(5)Cs3MnBi2 octahedra, and edges with two equivalent S(4)Cs2Bi3 square pyramids. The corner-sharing octahedral tilt angles range from 4-47°. In the fifth S site, S(5) is bonded to three equivalent Cs(1), one Mn(1), and two equivalent Bi(1) atoms to form distorted SCs3MnBi2 octahedra that share corners with two equivalent S(2)Cs3Bi3 octahedra, corners with four equivalent S(1)Cs3MnBi2 octahedra, corners with two equivalent S(4)Cs2Bi3 square pyramids,  an edgeedge with one S(2)Cs3Bi3 octahedra, edges with four equivalent S(5)Cs3MnBi2 octahedra, edges with three equivalent S(4)Cs2Bi3 square pyramids, and  a faceface with one S(1)Cs3MnBi2 octahedra. The corner-sharing octahedral tilt angles range from 2-73°.