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TlBrO4 is Iron carbide-derived structured and crystallizes in the orthorhombic Pnma space group. The structure is zero-dimensional and consists of four hypobromous acid;trihydrate molecules and four thallium molecules.
TlO3Br is Potassium chlorate-like structured and crystallizes in the trigonal R3m space group. The structure is three-dimensional. Tl1+ is bonded in a 9-coordinate geometry to nine equivalent O2- atoms. There are three shorter (2.95 Å) and six longer (3.23 Å) Tl–O bond lengths. O2- is bonded in a distorted single-bond geometry to three equivalent Tl1+ and one Br5+ atom. The O–Br bond length is 1.69 Å. Br5+ is bonded in a trigonal non-coplanar geometry to three equivalent O2- atoms.