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Pt2Si is Fluorite structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. Pt2- is bonded to four equivalent Si4+ atoms to form a mixture of edge and corner-sharing PtSi4 tetrahedra. All Pt–Si bond lengths are 2.49 Å. Si4+ is bonded in a body-centered cubic geometry to eight equivalent Pt2- atoms.
Pt2Si crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. there are two inequivalent Pt2- sites. In the first Pt2- site, Pt2- is bonded in a 5-coordinate geometry to five Si4+ atoms. There are one shorter (2.49 Å) and four longer (2.73 Å) Pt–Si bond lengths. In the second Pt2- site, Pt2- is bonded to four Si4+ atoms to form a mixture of distorted edge and corner-sharing PtSi4 tetrahedra. There are two shorter (2.39 Å) and two longer (2.57 Å) Pt–Si bond lengths. There are two inequivalent Si4+ sites. In the first Si4+ site, Si4+ is bonded in a 3-coordinate geometry to nine Pt2- atoms. In the second Si4+ site, Si4+ is bonded in a 9-coordinate geometry to nine Pt2- atoms.