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TmTl is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Tm is bonded in a body-centered cubic geometry to eight equivalent Tl atoms. All Tm–Tl bond lengths are 3.26 Å. Tl is bonded in a body-centered cubic geometry to eight equivalent Tm atoms.
TmTl(WO4)2 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Tm3+ is bonded in a 6-coordinate geometry to six O2- atoms. There are two shorter (2.24 Å) and four longer (2.28 Å) Tm–O bond lengths. W6+ is bonded to six O2- atoms to form a mixture of edge and corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles are 43°. There are a spread of W–O bond distances ranging from 1.84–2.12 Å. Tl1+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Tl–O bond distances ranging from 2.87–3.11 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a 4-coordinate geometry to two equivalent W6+ and two equivalent Tl1+ atoms. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Tm3+, one W6+, and one Tl1+ atom. In the third O2- site, O2- is bonded in a 3-coordinate geometry to one Tm3+, two equivalent W6+, and one Tl1+ atom. In the fourth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Tm3+, one W6+, and one Tl1+ atom.