Cs2CdBr4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one Br(1), three equivalent Br(2), and four equivalent Br(3) atoms. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to two equivalent Br(2), three equivalent Br(1), and four equivalent Br(3) atoms. Cd(1) is bonded in a tetrahedral geometry to one Br(1), one Br(2), and two equivalent Br(3) atoms. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded in a 5-coordinate geometry to one Cs(1), three equivalent Cs(2), and one Cd(1) atom. In the second Br site, Br(2) is bonded in a 6-coordinate geometry to two equivalent Cs(2), three equivalent Cs(1), and one Cd(1) atom. In the third Br site, Br(3) is bonded to two equivalent Cs(1), two equivalent Cs(2), and one Cd(1) atom to form a mixture of distorted edge, corner, and face-sharing BrCs4Cd square pyramids.
Cs2CdBr4 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to one Br(1), three equivalent Br(2), and four equivalent Br(3) atoms. The Cs(1)-Br(1) bond length is 3.67 Å. There is one shorter (3.96 Å) and two longer (4.04 Å) Cs(1)-Br(2) bond lengths. All Cs(1)-Br(3) bond lengths are 3.83 Å. In the second Cs site, Cs(2) is bonded in a 9-coordinate geometry to two equivalent Br(2), three equivalent Br(1), and four equivalent Br(3) atoms. There is one shorter (3.66 Å) and one longer (3.68 Å) Cs(2)-Br(2) bond length. There is one shorter (3.75 Å) and two longer (4.18 Å) Cs(2)-Br(1) bond lengths. There are two shorter (3.68 Å) and two longer (3.71 Å) Cs(2)-Br(3) bond lengths. Cd(1) is bonded in a tetrahedral geometry to one Br(1), one Br(2), and two equivalent Br(3) atoms. The Cd(1)-Br(1) bond length is 2.59 Å. The Cd(1)-Br(2) bond length is 2.62 Å. Both Cd(1)-Br(3) bond lengths are 2.60 Å. There are three inequivalent Br sites. In the first Br site, Br(1) is bonded in a 5-coordinate geometry to one Cs(1), three equivalent Cs(2), and one Cd(1) atom. In the second Br site, Br(2) is bonded in a 6-coordinate geometry to two equivalent Cs(2), three equivalent Cs(1), and one Cd(1) atom. In the third Br site, Br(3) is bonded to two equivalent Cs(1), two equivalent Cs(2), and one Cd(1) atom to form a mixture of distorted edge, corner, and face-sharing BrCs4Cd square pyramids.