Synthesis and Characterization of the Trisulfate Pb[S3O10] and Theoretical Analysis of H2S3O10

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Abstract
The reaction of (NH4)2PbCl6 and fuming sulfuric acid (65 % SO3) in a sealed glass tube at 250 °C led to colorless single crystals of Pb[S3O10] (orthorhombic, Pbcn, Z = 4, a = 10.9908(4), b = 8.5549(3), c = 8.0130(3) Å, V = 753.42(5) Å3). The compound shows a three‐dimensional linkage of the tenfold oxygen coordinated Pb2+ ions and exhibits the unusual trisulfate anion, [S3O10]2–, that consists of three vertex connected [SO4] tetrahedra. The distances S–O within the S–O–S bridges of the anion are remarkable asymmetric with distances of 155 and 169 pm, respectively. This structural feature is well reproduced by calculations on a PBE0/cc‐pVTZ and a MP2/cc‐pVTZ level of theory. Similar calculations allow also for an inspection of the yet unknown corresponding acid, H2S3O10. Also for this acid non‐symmetric S–O–S bridges are predicted. The thermal behavior of Pb[S3O10] is characterized by the loss of two equivalents of SO3 at low temperature and the decomposition of intermediate Pb[SO4] at higher temperature.

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