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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.