The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate‐Analogous Anion
Matthias Hämmer, Lkhamsuren Bayarjargal, Henning A. Höppe
Abstract
Abstract The first bismuth borosulfate (H 3 O)Bi[B(SO 4 ) 2 ] 4 is only the second featuring a three‐dimensional anion, the first tectosilicate‐analogous borosulfate synthesised solvothermally without a precursor (from Bi(NO 3 ) 3 ⋅5 H 2 O and B(OH) 3 in oleum); moreover, it is the first comprising two differently charged cations and crystallises in a new structure type in space group I (no. 82) (a=11.857(1), c=8.149(1) Å, 1947 refl., 111 param., wR2=0.037), confirmed by a second harmonic generation (SHG) measurement. The B(SO 4 ) 4 supertetrahedra are connected via all four sulfate tetrahedra resulting in a three‐dimensional anion with both H 3 O + and Bi 3+ cations in channels. Additionally, the crystal structure of a further bismuth borosulfate, Bi 2 [B 2 (SO 4 ) 6 ], is elucidated crystallising isotypically to the rare‐earth borosulfates R 2 [B 2 (SO 4 ) 6 ] in space group C2/c (No. 15) (a=13.568(2), b=11.490(2), c=11.106(2) Å, 3127 refl., 155 param., wR2=0.035). Moreover, the optical and thermal properties of both compounds are discussed.