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The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate-Analogous Anion - PubMed

  • ️Fri Jan 01 2021

The First Bismuth Borosulfates Comprising Oxonium and a Tectosilicate-Analogous Anion

Matthias Hämmer et al. Angew Chem Int Ed Engl. 2021.

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 Bi3+ 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.

Keywords: bismuth; borosulfate; crystal structure; oxonium; silicate-analogous.

© 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1

Crystal structure of (H3O)Bi[B(SO4)2]4: a) shows the borate (green) and sulfate (yellow) tetrahedra, b) shows the B(SO4)4 supertetrahedra neglecting the oxygen atoms (red) except the oxonium one; bismuth is depicted in grey and hydrogen in white; c) illustrates channels of supertetrahedra (dark green) forming Vierer and Achter rings along the [001] direction; the H3O+ and Bi3+ cations are located inside these channels; oxygen atoms are neglected except the oxonium one; d) depicts the anion of harmotome Ba2Al4Si12O32⋅12H2O [14] comprising AlO4/SiO4 tetrahedra (light blue) forming analogous Vierer and Achter rings.

Figure 2
Figure 2

a) Infrared spectra and b) thermogravimetric analyses of (H3O)Bi[B(SO4)2]4 and Bi2[B2(SO4)6].

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