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PtTl2 is Khatyrkite structured and crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. Pt2- is bonded in a 10-coordinate geometry to two equivalent Pt2- and eight equivalent Tl1+ atoms. Both Pt–Pt bond lengths are 2.84 Å. All Pt–Tl bond lengths are 3.00 Å. Tl1+ is bonded in a 4-coordinate geometry to four equivalent Pt2- atoms.
PtTl2(CN)4 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. Pt2+ is bonded in a distorted octahedral geometry to two equivalent Tl1+ and four C2+ atoms. Both Pt–Tl bond lengths are 3.14 Å. All Pt–C bond lengths are 2.00 Å. Tl1+ is bonded to one Pt2+ and five N3- atoms to form a mixture of distorted edge and corner-sharing TlPtN5 octahedra. The corner-sharing octahedra tilt angles range from 0–69°. There are a spread of Tl–N bond distances ranging from 2.80–3.03 Å. There are two inequivalent C2+ sites. In the first C2+ site, C2+ is bonded in a single-bond geometry to one Pt2+ and one N3- atom. The C–N bond length is 1.18 Å. In the second C2+ site, C2+ is bonded in a single-bond geometry to one Pt2+ and one N3- atom. The C–N bond length is 1.17 Å. There are two inequivalent N3- sites. In the first N3- site, N3- is bonded in a distorted single-bond geometry to two equivalent Tl1+ and one C2+ atom. In the second N3- site, N3- is bonded in a distorted single-bond geometry to three equivalent Tl1+ and one C2+ atom.
PtTl2 crystallizes in the orthorhombic Fmmm space group. The structure is three-dimensional. Pt2- is bonded to two equivalent Pt2- and four equivalent Tl1+ atoms to form distorted corner-sharing PtTl4Pt2 octahedra. The corner-sharing octahedra tilt angles range from 0–41°. Both Pt–Pt bond lengths are 2.82 Å. All Pt–Tl bond lengths are 2.78 Å. Tl1+ is bonded in a distorted bent 150 degrees geometry to two equivalent Pt2- atoms.