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TlClO3 is Ammonia-derived structured and crystallizes in the trigonal R3m space group. The structure is zero-dimensional and consists of three ramor molecules and three ClO3 clusters. In each ClO3 cluster, O is bonded in a single-bond geometry to one Cl atom. The O–Cl bond length is 1.51 Å. Cl is bonded in a trigonal non-coplanar geometry to three equivalent O atoms.
TlClO4 is Silicon tetrafluoride-derived structured and crystallizes in the cubic F-43m space group. The structure is zero-dimensional and consists of four thallium molecules and four ClO4 clusters. In each ClO4 cluster, O is bonded in a single-bond geometry to one Cl atom. The O–Cl bond length is 1.47 Å. Cl is bonded in a tetrahedral geometry to four equivalent O atoms.