CaMn2As2 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 Mn(1)As4 tetrahedra, edges with six equivalent Ca(1)As6 octahedra, and edges with six equivalent Mn(1)As4 tetrahedra. Mn(1) is bonded to four equivalent As(1) atoms to form MnAs4 tetrahedra that share corners with six equivalent Ca(1)As6 octahedra, corners with six equivalent Mn(1)As4 tetrahedra, edges with three equivalent Ca(1)As6 octahedra, and edges with three equivalent Mn(1)As4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-51°. As(1) is bonded to three equivalent Ca(1) and four equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing AsCa3Mn4 pentagonal bipyramids.
CaMn2As2 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 Mn(1)As4 tetrahedra, edges with six equivalent Ca(1)As6 octahedra, and edges with six equivalent Mn(1)As4 tetrahedra. All Ca(1)-As(1) bond lengths are 2.99 Å. Mn(1) is bonded to four equivalent As(1) atoms to form MnAs4 tetrahedra that share corners with six equivalent Ca(1)As6 octahedra, corners with six equivalent Mn(1)As4 tetrahedra, edges with three equivalent Ca(1)As6 octahedra, and edges with three equivalent Mn(1)As4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-51°. There is one shorter (2.41 Å) and three longer (2.44 Å) Mn(1)-As(1) bond lengths. As(1) is bonded to three equivalent Ca(1) and four equivalent Mn(1) atoms to form a mixture of distorted corner and edge-sharing AsCa3Mn4 pentagonal bipyramids.