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Rh2As is Fluorite structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Rh is bonded to four equivalent As atoms to form a mixture of distorted corner and edge-sharing RhAs4 tetrahedra. All Rh–As bond lengths are 2.49 Å. As is bonded in a body-centered cubic geometry to eight equivalent Rh atoms.
Rh2As is Cotunnite structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are two inequivalent Rh sites. In the first Rh site, Rh is bonded to four equivalent As atoms to form a mixture of distorted edge and corner-sharing RhAs4 tetrahedra. There are a spread of Rh–As bond distances ranging from 2.42–2.54 Å. In the second Rh site, Rh is bonded in a 3-coordinate geometry to five equivalent As atoms. There are a spread of Rh–As bond distances ranging from 2.48–2.90 Å. As is bonded in a 9-coordinate geometry to nine Rh atoms.