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TlNO2 crystallizes in the trigonal P3_121 space group. The structure is three-dimensional. Tl1+ is bonded in a 8-coordinate geometry to eight equivalent O2- atoms. There are a spread of Tl–O bond distances ranging from 2.94–3.37 Å. N3+ is bonded in a bent 120 degrees geometry to two equivalent O2- atoms. Both N–O bond lengths are 1.27 Å. O2- is bonded in a distorted single-bond geometry to four equivalent Tl1+ and one N3+ atom.
TlNO2 crystallizes in the triclinic P1 space group. The structure is three-dimensional. Tl1+ is bonded in a 7-coordinate geometry to five O2- atoms. There are a spread of Tl–O bond distances ranging from 2.95–3.23 Å. N3+ is bonded in a bent 120 degrees geometry to two O2- atoms. Both N–O bond lengths are 1.27 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to three equivalent Tl1+ and one N3+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to two equivalent Tl1+ and one N3+ atom.
Tl5NO5 crystallizes in the monoclinic Pm space group. The structure is two-dimensional and consists of one Tl5NO5 sheet oriented in the (0, 0, 1) direction. there are three inequivalent Tl1+ sites. In the first Tl1+ site, Tl1+ is bonded in a water-like geometry to two equivalent O2- atoms. Both Tl–O bond lengths are 2.38 Å. In the second Tl1+ site, Tl1+ is bonded in a 2-coordinate geometry to two O2- atoms. There are one shorter (2.53 Å) and one longer (2.73 Å) Tl–O bond lengths. In the third Tl1+ site, Tl1+ is bonded in a water-like geometry to two equivalent O2- atoms. There are one shorter (2.41 Å) and one longer (2.45 Å) Tl–O bond lengths. N5+ is bonded in a bent 120 degrees geometry to two O2- atoms. There is one shorter (1.21 Å) and one longer (1.44 Å) N–O bond length. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to one N5+ and one O2- atom. The O–O bond length is 1.40 Å. In the second O2- site, O2- is bonded to four Tl1+ atoms to form corner-sharing OTl4 tetrahedra. In the third O2- site, O2- is bonded in a single-bond geometry to one N5+ atom. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to two equivalent Tl1+ and one O2- atom.