CaCd2As2 crystallizes in the trigonal P-3m1 space group. Ca(1) is bonded to six equivalent As(1) atoms to form CaAs6 octahedra that share corners with twelve equivalent Cd(1)As4 tetrahedra, edges with six equivalent Ca(1)As6 octahedra, and edges with six equivalent Cd(1)As4 tetrahedra. Cd(1) is bonded to four equivalent As(1) atoms to form CdAs4 tetrahedra that share corners with six equivalent Ca(1)As6 octahedra, corners with six equivalent Cd(1)As4 tetrahedra, edges with three equivalent Ca(1)As6 octahedra, and edges with three equivalent Cd(1)As4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-56°. As(1) is bonded to three equivalent Ca(1) and four equivalent Cd(1) atoms to form a mixture of distorted edge and corner-sharing AsCa3Cd4 pentagonal bipyramids.
CaCd2As2 crystallizes in the trigonal P-3m1 space group. Ca(1) is bonded to six equivalent As(1) atoms to form CaAs6 octahedra that share corners with twelve equivalent Cd(1)As4 tetrahedra, edges with six equivalent Ca(1)As6 octahedra, and edges with six equivalent Cd(1)As4 tetrahedra. All Ca(1)-As(1) bond lengths are 3.07 Å. Cd(1) is bonded to four equivalent As(1) atoms to form CdAs4 tetrahedra that share corners with six equivalent Ca(1)As6 octahedra, corners with six equivalent Cd(1)As4 tetrahedra, edges with three equivalent Ca(1)As6 octahedra, and edges with three equivalent Cd(1)As4 tetrahedra. The corner-sharing octahedral tilt angles range from 14-56°. There are three shorter (2.71 Å) and one longer (2.85 Å) Cd(1)-As(1) bond length. As(1) is bonded to three equivalent Ca(1) and four equivalent Cd(1) atoms to form a mixture of distorted edge and corner-sharing AsCa3Cd4 pentagonal bipyramids.