Ca5As3 crystallizes in the hexagonal P6_3/mcm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to six equivalent As(1) atoms to form a mixture of distorted corner, edge, and face-sharing CaAs6 octahedra. The corner-sharing octahedral tilt angles are 35°. In the second Ca site, Ca(2) is bonded in a 3-coordinate geometry to five equivalent As(1) atoms. As(1) is bonded in a 9-coordinate geometry to four equivalent Ca(1) and five equivalent Ca(2) atoms.
Ca5As3 crystallizes in the hexagonal P6_3/mcm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded to six equivalent As(1) atoms to form a mixture of distorted corner, edge, and face-sharing CaAs6 octahedra. The corner-sharing octahedral tilt angles are 35°. All Ca(1)-As(1) bond lengths are 3.13 Å. In the second Ca site, Ca(2) is bonded in a 3-coordinate geometry to five equivalent As(1) atoms. There are a spread of Ca(2)-As(1) bond distances ranging from 2.91-3.58 Å. As(1) is bonded in a 9-coordinate geometry to four equivalent Ca(1) and five equivalent Ca(2) atoms.