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(NdAs)2AuAs crystallizes in the tetragonal P4/mmm space group. The structure is zero-dimensional and consists of two arsanylidyneneodymium molecules, one arsenic molecule, and one gold molecule.
NdAuAs2 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Nd3+ is bonded in a 8-coordinate geometry to eight As3- atoms. There are a spread of Nd–As bond distances ranging from 3.03–3.26 Å. Au3+ is bonded to four equivalent As3- atoms to form a mixture of distorted corner and edge-sharing AuAs4 tetrahedra. There are three shorter (2.81 Å) and one longer (2.83 Å) Au–As bond lengths. There are two inequivalent As3- sites. In the first As3- site, As3- is bonded in a 6-coordinate geometry to four equivalent Nd3+ and two equivalent As3- atoms. Both As–As bond lengths are 2.64 Å. In the second As3- site, As3- is bonded in a 8-coordinate geometry to four equivalent Nd3+ and four equivalent Au3+ atoms.