Cs2ZnI4 crystallizes in the monoclinic P2_1/c 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(2), two equivalent I(3), two equivalent I(4), and three equivalent I(1) atoms. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to one I(1), two equivalent I(2), two equivalent I(3), and two equivalent I(4) atoms. Zn(1) is bonded in a tetrahedral geometry to one I(1), one I(2), one I(3), and one I(4) atom. There are four inequivalent I sites. In the first I site, I(1) is bonded in a 5-coordinate geometry to one Cs(2), three equivalent Cs(1), and one Zn(1) atom. In the second I site, I(2) is bonded in a 1-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and one Zn(1) atom. In the third I site, I(3) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Zn(1) atom. In the fourth I site, I(4) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Zn(1) atom.
Cs2ZnI4 crystallizes in the monoclinic P2_1/c 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(2), two equivalent I(3), two equivalent I(4), and three equivalent I(1) atoms. There is one shorter (3.82 Å) and one longer (3.96 Å) Cs(1)-I(2) bond length. There is one shorter (3.91 Å) and one longer (3.96 Å) Cs(1)-I(3) bond length. There is one shorter (3.90 Å) and one longer (3.96 Å) Cs(1)-I(4) bond length. There is one shorter (3.90 Å) and two longer (4.31 Å) Cs(1)-I(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 7-coordinate geometry to one I(1), two equivalent I(2), two equivalent I(3), and two equivalent I(4) atoms. The Cs(2)-I(1) bond length is 4.04 Å. There is one shorter (4.23 Å) and one longer (4.24 Å) Cs(2)-I(2) bond length. There is one shorter (4.03 Å) and one longer (4.22 Å) Cs(2)-I(3) bond length. There is one shorter (4.03 Å) and one longer (4.22 Å) Cs(2)-I(4) bond length. Zn(1) is bonded in a tetrahedral geometry to one I(1), one I(2), one I(3), and one I(4) atom. The Zn(1)-I(1) bond length is 2.62 Å. The Zn(1)-I(2) bond length is 2.62 Å. The Zn(1)-I(3) bond length is 2.61 Å. The Zn(1)-I(4) bond length is 2.61 Å. There are four inequivalent I sites. In the first I site, I(1) is bonded in a 5-coordinate geometry to one Cs(2), three equivalent Cs(1), and one Zn(1) atom. In the second I site, I(2) is bonded in a 1-coordinate geometry to two equivalent Cs(1), two equivalent Cs(2), and one Zn(1) atom. In the third I site, I(3) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Zn(1) atom. In the fourth I site, I(4) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Zn(1) atom.