The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate‐Analogous Anion. Issue 3 (12th November 2020)

• Record Type: Journal Article
• Authors: Hämmer, Matthias; Bayarjargal, Lkhamsuren; Höppe, Henning A.
• Is Part Of: Angewandte Chemie international edition. Volume 60:Issue 3(2021)
• Page Start: 1503
• Page End: 1506
• Publication Date: 2020-11-12
• Subjects: bismuth -- borosulfate -- crystal structure -- oxonium -- silicate-analogous; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202011786
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The first bismuth borosulfate (H3 O)Bi[B(SO4 )2 ]4 is only the second featuring a three‐dimensional anion, the first tectosilicate‐analogous borosulfate synthesised solvothermally without a precursor (from Bi(NO3 )3 ⋅5 H2 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 4 ‾ (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(SO4 )4 supertetrahedra are connected via all four sulfate tetrahedra resulting in a three‐dimensional anion with both H3 O + and Bi 3+ cations in channels. Additionally, the crystal structure of a further bismuth borosulfate, Bi2 [B2 (SO4 )6 ], is elucidated crystallising isotypically to the rare‐earth borosulfates R2 [B2 (SO4 )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. Abstract : The first tectosilicate‐analogous oxonium–bismuth borosulfate obtained from the reaction of oleum with bismuth nitrate and boric acid decomposes to the first bismuth borosulfate—a ring‐silicate‐analogous one—delivering exciting insights in the chemistry and the crystal structures of this still expanding material class.