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Cd3As2 crystallizes in the cubic Pn-3m space group. The structure is three-dimensional. Cd2+ is bonded to four equivalent As3- atoms to form a mixture of corner and edge-sharing CdAs4 tetrahedra. All Cd–As bond lengths are 2.81 Å. As3- is bonded in a 6-coordinate geometry to six equivalent Cd2+ atoms.
CdAs crystallizes in the orthorhombic Pbca space group. The structure is three-dimensional. Cd2+ is bonded to four equivalent As2- atoms to form a mixture of edge and corner-sharing CdAs4 tetrahedra. There are a spread of Cd–As bond distances ranging from 2.69–2.99 Å. As2- is bonded in a 5-coordinate geometry to four equivalent Cd2+ and one As2- atom. The As–As bond length is 2.48 Å.