Cs2NiAs2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to two equivalent Ni(1) and six equivalent As(1) atoms. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to six equivalent As(1) atoms. Ni(1) is bonded in a 6-coordinate geometry to two equivalent Cs(1) and four equivalent As(1) atoms. As(1) is bonded in a 9-coordinate geometry to three equivalent Cs(1), three equivalent Cs(2), two equivalent Ni(1), and one As(1) atom.
Cs2NiAs2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 8-coordinate geometry to two equivalent Ni(1) and six equivalent As(1) atoms. Both Cs(1)-Ni(1) bond lengths are 3.42 Å. There are four shorter (3.73 Å) and two longer (3.82 Å) Cs(1)-As(1) bond lengths. In the second Cs site, Cs(2) is bonded in a 6-coordinate geometry to six equivalent As(1) atoms. There are two shorter (3.61 Å) and four longer (3.89 Å) Cs(2)-As(1) bond lengths. Ni(1) is bonded in a 6-coordinate geometry to two equivalent Cs(1) and four equivalent As(1) atoms. All Ni(1)-As(1) bond lengths are 2.35 Å. As(1) is bonded in a 9-coordinate geometry to three equivalent Cs(1), three equivalent Cs(2), two equivalent Ni(1), and one As(1) atom. The As(1)-As(1) bond length is 2.41 Å.