CsSbSI2 crystallizes in the orthorhombic Pmma space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to four equivalent S(2), two equivalent I(2), and four equivalent I(1) atoms. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to two equivalent I(2), four equivalent I(1), and four equivalent I(3) atoms. Sb(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), one I(2), one I(3), and two equivalent I(1) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded in a bent 150 degrees geometry to two equivalent Sb(1) atoms. In the second S site, S(2) is bonded in a linear geometry to four equivalent Cs(1) and two equivalent Sb(1) atoms. There are three inequivalent I sites. In the first I site, I(1) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms to form a mixture of edge, corner, and face-sharing ICs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 4-64°. In the second I site, I(2) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms to form a mixture of edge, corner, and face-sharing ICs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 57-61°. In the third I site, I(3) is bonded to four equivalent Cs(2) and two equivalent Sb(1) atoms to form a mixture of edge, corner, and face-sharing ICs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 1-64°.
CsSbSI2 crystallizes in the orthorhombic Pmma space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to four equivalent S(2), two equivalent I(2), and four equivalent I(1) atoms. All Cs(1)-S(2) bond lengths are 4.21 Å. Both Cs(1)-I(2) bond lengths are 4.13 Å. There are two shorter (3.99 Å) and two longer (4.01 Å) Cs(1)-I(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 10-coordinate geometry to two equivalent I(2), four equivalent I(1), and four equivalent I(3) atoms. Both Cs(2)-I(2) bond lengths are 4.26 Å. There are two shorter (4.11 Å) and two longer (4.27 Å) Cs(2)-I(1) bond lengths. All Cs(2)-I(3) bond lengths are 4.20 Å. Sb(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), one I(2), one I(3), and two equivalent I(1) atoms. The Sb(1)-S(1) bond length is 2.52 Å. The Sb(1)-S(2) bond length is 2.50 Å. The Sb(1)-I(2) bond length is 3.24 Å. The Sb(1)-I(3) bond length is 3.41 Å. Both Sb(1)-I(1) bond lengths are 3.11 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a bent 150 degrees geometry to two equivalent Sb(1) atoms. In the second S site, S(2) is bonded in a linear geometry to four equivalent Cs(1) and two equivalent Sb(1) atoms. There are three inequivalent I sites. In the first I site, I(1) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms to form a mixture of edge, corner, and face-sharing ICs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 4-64°. In the second I site, I(2) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms to form a mixture of edge, corner, and face-sharing ICs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 57-61°. In the third I site, I(3) is bonded to four equivalent Cs(2) and two equivalent Sb(1) atoms to form a mixture of edge, corner, and face-sharing ICs4Sb2 octahedra. The corner-sharing octahedral tilt angles range from 1-64°.