| Institution: | 1. University of Innsbruck, Institute of General Inorganic and Theoretical Chemistry, Innrain 80–82, 6020 Innsbruck, Austria;2. Universität des Saarlandes, Anorganische Festkörperchemie, Campus C4 1, 66123 Saarbrücken, Germany
Westfälische Wilhelms-Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstrasse 30, 48149 Münster, Germany;3. Institute of Physical Chemistry, University of Cologne, Greinstrasse 4–6, 50939 Cologne, Germany;4. Westfälische Wilhelms-Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstrasse 30, 48149 Münster, Germany;5. Institute of Inorganic Chemistry, University of Cologne, Greinstrasse 6, 50939 Cologne, Germany |
| Abstract: | Borosulfates are compounds analogous to silicates, with heteropolyanionic subunits of vertex-linked (SO4)- and (BO4)-tetrahedra. In contrast to the immense structural diversity of silicates, the number of borosulfates is yet very limited and the extent of their properties is still unknown. This is particularly true for representatives with phyllosilicate and tectosilicate analogue anionic substructures. Herein, we present NiB2(SO4)4] and CoB2(SO4)4], two new borosulfates with phyllosilicate analogue topology. While the anionic subunits of both structures are homeotypic, the positions of the charge compensating cations differ significantly: NiII is located between the borosulfate layers, while CoII—in contrast—is embedded within the layer. Detailed analysis of these two structures based on single-crystal X-ray diffraction, magnetochemical investigations, X-ray photoelectron spectroscopy, and quantum chemical calculations, unveiled the reasons for this finding. By in silico comparison with other divalent borosulfates, we uncovered systematic trends for phyllosilicate analogues leading to the prediction of new species. |
