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PtAs2 is pyrite structured and crystallizes in the cubic Pa-3 space group. The structure is three-dimensional. Pt2- is bonded to six equivalent As1+ atoms to form corner-sharing PtAs6 octahedra. The corner-sharing octahedral tilt angles are 64°. All Pt–As bond lengths are 2.53 Å. As1+ is bonded in a trigonal planar geometry to three equivalent Pt2- atoms.
Pt3As crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Pt+0.67+ is bonded in a see-saw-like geometry to four equivalent As2- atoms. There are two shorter (2.79 Å) and two longer (2.88 Å) Pt–As bond lengths. As2- is bonded to twelve equivalent Pt+0.67+ atoms to form a mixture of face and corner-sharing AsPt12 cuboctahedra.