Cd3AsCl3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one As(1), one Cl(2), and four equivalent Cl(1) atoms to form distorted CdAsCl5 octahedra that share corners with four equivalent Cd(2)As2Cl4 octahedra, corners with four equivalent Cd(1)AsCl5 octahedra, and edges with two equivalent Cd(2)As2Cl4 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. In the second Cd site, Cd(2) is bonded to two equivalent As(1), two equivalent Cl(1), and two equivalent Cl(2) atoms to form distorted CdAs2Cl4 octahedra that share corners with four equivalent Cd(1)AsCl5 octahedra, edges with two equivalent Cd(2)As2Cl4 octahedra, and edges with two equivalent Cd(1)AsCl5 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. In the third Cd site, Cd(3) is bonded in a rectangular see-saw-like geometry to one As(1), one Cl(2), and two equivalent Cl(1) atoms. As(1) is bonded to one Cd(1), one Cd(3), and two equivalent Cd(2) atoms to form corner-sharing AsCd4 tetrahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 4-coordinate geometry to one Cd(2), one Cd(3), and two equivalent Cd(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted bent 120 degrees geometry to one Cd(1), one Cd(3), and two equivalent Cd(2) atoms.
Cd3AsCl3 crystallizes in the orthorhombic Pnma space group. There are three inequivalent Cd sites. In the first Cd site, Cd(1) is bonded to one As(1), one Cl(2), and four equivalent Cl(1) atoms to form distorted CdAsCl5 octahedra that share corners with four equivalent Cd(2)As2Cl4 octahedra, corners with four equivalent Cd(1)AsCl5 octahedra, and edges with two equivalent Cd(2)As2Cl4 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. The Cd(1)-As(1) bond length is 2.56 Å. The Cd(1)-Cl(2) bond length is 2.53 Å. There are two shorter (2.76 Å) and two longer (3.13 Å) Cd(1)-Cl(1) bond lengths. In the second Cd site, Cd(2) is bonded to two equivalent As(1), two equivalent Cl(1), and two equivalent Cl(2) atoms to form distorted CdAs2Cl4 octahedra that share corners with four equivalent Cd(1)AsCl5 octahedra, edges with two equivalent Cd(2)As2Cl4 octahedra, and edges with two equivalent Cd(1)AsCl5 octahedra. The corner-sharing octahedral tilt angles range from 48-56°. Both Cd(2)-As(1) bond lengths are 2.54 Å. Both Cd(2)-Cl(1) bond lengths are 3.10 Å. Both Cd(2)-Cl(2) bond lengths are 3.17 Å. In the third Cd site, Cd(3) is bonded in a rectangular see-saw-like geometry to one As(1), one Cl(2), and two equivalent Cl(1) atoms. The Cd(3)-As(1) bond length is 2.53 Å. The Cd(3)-Cl(2) bond length is 2.65 Å. Both Cd(3)-Cl(1) bond lengths are 2.57 Å. As(1) is bonded to one Cd(1), one Cd(3), and two equivalent Cd(2) atoms to form corner-sharing AsCd4 tetrahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 4-coordinate geometry to one Cd(2), one Cd(3), and two equivalent Cd(1) atoms. In the second Cl site, Cl(2) is bonded in a distorted bent 120 degrees geometry to one Cd(1), one Cd(3), and two equivalent Cd(2) atoms.