CsSbSI2 crystallizes in the tetragonal P4_222 space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent I(4), four equivalent I(1), and four equivalent I(2) atoms. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent I(1), two equivalent I(2), two equivalent I(3), and two equivalent I(4) atoms. In the third Cs site, Cs(3) is bonded to two equivalent S(1), four equivalent S(2), two equivalent I(4), and four equivalent I(3) atoms to form face-sharing CsS6I6 cuboctahedra. Sb(1) is bonded in a 5-coordinate geometry to one S(1), one S(2), one I(1), 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 linear geometry to one Cs(3) and two equivalent Sb(1) atoms. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cs(3) and two equivalent Sb(1) atoms. There are four inequivalent I sites. In the first I site, I(3) is bonded to two equivalent Cs(2), two equivalent Cs(3), and two equivalent Sb(1) atoms to form a mixture of distorted corner, face, and edge-sharing ICs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 56-63°. In the second I site, I(4) is bonded to one Cs(1), one Cs(3), two equivalent Cs(2), and two equivalent Sb(1) atoms to form a mixture of corner and face-sharing ICs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 0-58°. In the third I site, I(1) is bonded in a distorted see-saw-like geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms. In the fourth I site, I(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cs(1) and two equivalent Cs(2) atoms.
CsSbSI2 crystallizes in the tetragonal P4_222 space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent I(4), four equivalent I(1), and four equivalent I(2) atoms. Both Cs(1)-I(4) bond lengths are 4.27 Å. All Cs(1)-I(1) bond lengths are 4.53 Å. All Cs(1)-I(2) bond lengths are 4.03 Å. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent I(1), two equivalent I(2), two equivalent I(3), and two equivalent I(4) atoms. Both Cs(2)-I(1) bond lengths are 3.95 Å. Both Cs(2)-I(2) bond lengths are 4.13 Å. Both Cs(2)-I(3) bond lengths are 3.89 Å. Both Cs(2)-I(4) bond lengths are 4.26 Å. In the third Cs site, Cs(3) is bonded to two equivalent S(1), four equivalent S(2), two equivalent I(4), and four equivalent I(3) atoms to form face-sharing CsS6I6 cuboctahedra. Both Cs(3)-S(1) bond lengths are 4.10 Å. All Cs(3)-S(2) bond lengths are 3.80 Å. Both Cs(3)-I(4) bond lengths are 4.23 Å. All Cs(3)-I(3) bond lengths are 4.26 Å. Sb(1) is bonded in a 5-coordinate geometry to one S(1), one S(2), one I(1), one I(3), and one I(4) atom. The Sb(1)-S(1) bond length is 2.55 Å. The Sb(1)-S(2) bond length is 2.54 Å. The Sb(1)-I(1) bond length is 3.09 Å. The Sb(1)-I(3) bond length is 3.04 Å. The Sb(1)-I(4) bond length is 3.24 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted linear geometry to one Cs(3) and two equivalent Sb(1) atoms. In the second S site, S(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cs(3) and two equivalent Sb(1) atoms. There are four inequivalent I sites. In the first I site, I(3) is bonded to two equivalent Cs(2), two equivalent Cs(3), and two equivalent Sb(1) atoms to form a mixture of distorted corner, face, and edge-sharing ICs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 56-63°. In the second I site, I(4) is bonded to one Cs(1), one Cs(3), two equivalent Cs(2), and two equivalent Sb(1) atoms to form a mixture of corner and face-sharing ICs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 0-58°. In the third I site, I(1) is bonded in a distorted see-saw-like geometry to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms. In the fourth I site, I(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Cs(1) and two equivalent Cs(2) atoms.