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SrTl2 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Sr is bonded in a 12-coordinate geometry to twelve equivalent Tl atoms. There are six shorter (3.46 Å) and six longer (3.93 Å) Sr–Tl bond lengths. Tl is bonded in a 10-coordinate geometry to six equivalent Sr and four equivalent Tl atoms. There are three shorter (3.12 Å) and one longer (3.39 Å) Tl–Tl bond lengths.
SrTl2(PO3)4 crystallizes in the tetragonal I-4 space group. The structure is three-dimensional. Sr2+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are four shorter (2.61 Å) and four longer (2.72 Å) Sr–O bond lengths. Tl1+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Tl–O bond distances ranging from 2.91–3.43 Å. P5+ is bonded to four O2- atoms to form corner-sharing PO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.50–1.63 Å. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Tl1+ and two equivalent P5+ atoms. In the second O2- site, O2- is bonded in a distorted single-bond geometry to one Sr2+, two equivalent Tl1+, and one P5+ atom. In the third O2- site, O2- is bonded in a distorted single-bond geometry to one Sr2+, two equivalent Tl1+, and one P5+ atom.