Ca2CdAs2 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent As(1) and three equivalent As(2) atoms to form a mixture of distorted corner and edge-sharing CaAs5 square pyramids. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to one As(2) and four equivalent As(1) atoms. Cd(1) is bonded in a 4-coordinate geometry to two equivalent As(1) and two equivalent As(2) atoms. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to two equivalent Ca(1), four equivalent Ca(2), and two equivalent Cd(1) atoms. In the second As site, As(2) is bonded to one Ca(2), three equivalent Ca(1), and two equivalent Cd(1) atoms to form a mixture of distorted corner and edge-sharing AsCa4Cd2 octahedra. The corner-sharing octahedral tilt angles are 76°.
Ca2CdAs2 crystallizes in the orthorhombic Cmc2_1 space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to two equivalent As(1) and three equivalent As(2) atoms to form a mixture of distorted corner and edge-sharing CaAs5 square pyramids. Both Ca(1)-As(1) bond lengths are 3.13 Å. There are two shorter (2.97 Å) and one longer (3.08 Å) Ca(1)-As(2) bond length. In the second Ca site, Ca(2) is bonded in a 5-coordinate geometry to one As(2) and four equivalent As(1) atoms. The Ca(2)-As(2) bond length is 2.94 Å. There are two shorter (3.04 Å) and two longer (3.09 Å) Ca(2)-As(1) bond lengths. Cd(1) is bonded in a 4-coordinate geometry to two equivalent As(1) and two equivalent As(2) atoms. There is one shorter (2.75 Å) and one longer (2.83 Å) Cd(1)-As(1) bond length. Both Cd(1)-As(2) bond lengths are 2.66 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded in a 8-coordinate geometry to two equivalent Ca(1), four equivalent Ca(2), and two equivalent Cd(1) atoms. In the second As site, As(2) is bonded to one Ca(2), three equivalent Ca(1), and two equivalent Cd(1) atoms to form a mixture of distorted corner and edge-sharing AsCa4Cd2 octahedra. The corner-sharing octahedral tilt angles are 76°.