CsSbSI2 crystallizes in the orthorhombic P222_1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to two equivalent I(1), two equivalent I(3), two equivalent I(4), and three equivalent I(2) atoms. In the second Cs site, Cs(2) is bonded in a 11-coordinate geometry to two equivalent S(1), three equivalent S(2), two equivalent I(1), two equivalent I(3), and two equivalent I(4) atoms. Sb(1) is bonded in a 5-coordinate geometry to one S(1), one S(2), one I(1), one I(2), one I(3), and one I(4) atom. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted see-saw-like geometry to two equivalent Cs(2) and two equivalent Sb(1) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to three equivalent Cs(2) and two equivalent Sb(1) atoms. There are four inequivalent I sites. In the first I site, I(1) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms. In the second I site, I(2) is bonded to three equivalent Cs(1) and two equivalent Sb(1) atoms to form distorted ICs3Sb2 square pyramids that share corners with four equivalent I(3)Cs4Sb2 octahedra, corners with four equivalent I(4)Cs4Sb2 octahedra, corners with two equivalent I(2)Cs3Sb2 square pyramids, edges with two equivalent I(3)Cs4Sb2 octahedra, edges with two equivalent I(4)Cs4Sb2 octahedra, and edges with two equivalent I(2)Cs3Sb2 square pyramids. The corner-sharing octahedral tilt angles range from 54-60°. In the third I site, I(3) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms to form distorted ICs4Sb2 octahedra that share corners with four equivalent I(3)Cs4Sb2 octahedra, corners with four equivalent I(2)Cs3Sb2 square pyramids, edges with two equivalent I(4)Cs4Sb2 octahedra, edges with two equivalent I(2)Cs3Sb2 square pyramids, and faces with two equivalent I(4)Cs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 55-59°. In the fourth I site, I(4) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms to form distorted ICs4Sb2 octahedra that share corners with four equivalent I(4)Cs4Sb2 octahedra, corners with four equivalent I(2)Cs3Sb2 square pyramids, edges with two equivalent I(3)Cs4Sb2 octahedra, edges with two equivalent I(2)Cs3Sb2 square pyramids, and faces with two equivalent I(3)Cs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 55-59°.
CsSbSI2 crystallizes in the orthorhombic P222_1 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 9-coordinate geometry to two equivalent I(1), two equivalent I(3), two equivalent I(4), and three equivalent I(2) atoms. Both Cs(1)-I(1) bond lengths are 4.44 Å. Both Cs(1)-I(3) bond lengths are 4.00 Å. Both Cs(1)-I(4) bond lengths are 4.01 Å. There is one shorter (3.94 Å) and two longer (4.24 Å) Cs(1)-I(2) bond lengths. In the second Cs site, Cs(2) is bonded in a 11-coordinate geometry to two equivalent S(1), three equivalent S(2), two equivalent I(1), two equivalent I(3), and two equivalent I(4) atoms. Both Cs(2)-S(1) bond lengths are 3.69 Å. There is one shorter (3.56 Å) and two longer (4.19 Å) Cs(2)-S(2) bond lengths. Both Cs(2)-I(1) bond lengths are 4.09 Å. Both Cs(2)-I(3) bond lengths are 4.08 Å. Both Cs(2)-I(4) bond lengths are 4.08 Å. Sb(1) is bonded in a 5-coordinate geometry to one S(1), one S(2), one I(1), one I(2), one I(3), and one I(4) atom. The Sb(1)-S(1) bond length is 2.56 Å. The Sb(1)-S(2) bond length is 2.51 Å. The Sb(1)-I(1) bond length is 3.01 Å. The Sb(1)-I(2) bond length is 3.41 Å. The Sb(1)-I(3) bond length is 3.13 Å. The Sb(1)-I(4) bond length is 3.53 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted see-saw-like geometry to two equivalent Cs(2) and two equivalent Sb(1) atoms. In the second S site, S(2) is bonded in a 3-coordinate geometry to three equivalent Cs(2) and two equivalent Sb(1) atoms. There are four inequivalent I sites. In the first I site, I(1) is bonded in a 6-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms. In the second I site, I(2) is bonded to three equivalent Cs(1) and two equivalent Sb(1) atoms to form distorted ICs3Sb2 square pyramids that share corners with four equivalent I(3)Cs4Sb2 octahedra, corners with four equivalent I(4)Cs4Sb2 octahedra, corners with two equivalent I(2)Cs3Sb2 square pyramids, edges with two equivalent I(3)Cs4Sb2 octahedra, edges with two equivalent I(4)Cs4Sb2 octahedra, and edges with two equivalent I(2)Cs3Sb2 square pyramids. The corner-sharing octahedral tilt angles range from 54-60°. In the third I site, I(3) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms to form distorted ICs4Sb2 octahedra that share corners with four equivalent I(3)Cs4Sb2 octahedra, corners with four equivalent I(2)Cs3Sb2 square pyramids, edges with two equivalent I(4)Cs4Sb2 octahedra, edges with two equivalent I(2)Cs3Sb2 square pyramids, and faces with two equivalent I(4)Cs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 55-59°. In the fourth I site, I(4) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms to form distorted ICs4Sb2 octahedra that share corners with four equivalent I(4)Cs4Sb2 octahedra, corners with four equivalent I(2)Cs3Sb2 square pyramids, edges with two equivalent I(3)Cs4Sb2 octahedra, edges with two equivalent I(2)Cs3Sb2 square pyramids, and faces with two equivalent I(3)Cs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 55-59°.