Mössbauer Spectroscopy on Antimony Borosulfates Reveals Weak Coordination Behavior

Angewandte Chemie International Edition, vol. 65, pp. e21198

Abstract

Abstract With M III M I [B(SO 4 ) 2 ] 4 (M III = Bi 3+ , Sb 3+ , Lu 3+ ; M I = H 3 O + , NO 2 + , Li + , Na + , K + , Rb + , Cs + ), we recently described the first modular system within borosulfate chemistry comprising a three‐dimensional anion. Herein, we shed light on the respective series of antimony compounds SbX[B(SO 4 ) 2 ] 4 (X = Li + , Na + , K + , Rb + , Cs + , Ag + , Tl + , NO + , NH 4 + ). While maintaining the same anionic topology, the compounds crystallize in the space groups I (no. 82), P (no. 81), and C 2 (no. 5) and are strongly influenced by the lone pair of antimony as well as the size of the monovalent cations. In the course of this investigation SbX[B 4 O 2 (SO 4 ) 6 ] (X = Li + , Na + ) were discovered. This borosulfate with a one‐dimensional anion comprising B─O─B bridges crystallizes in the space group Pnma (no. 62) and features a new structure type. 121 Sb Mössbauer spectra revealed negative isomer shifts of almost −22 mm·s −1 not observed before and hinting towards a very weak coordination behavior of the borosulfate anion. The spectra are confirmed by DFT calculations. Furthermore, single crystal X‐ray diffraction, infrared spectroscopy, thermal analysis, and temperature programmed X‐ray diffraction experiments were carried out.

Authors 7

1. Erich Turgunbajew

   University of Augsburg

   Affiliation as printed

   Lehrstuhl für Festkörperchemie Universität Augsburg Universitätsstraße 1 86159 Augsburg Germany

2. Gwendolyn Buchner

   University of Augsburg

   Affiliation as printed

   Lehrstuhl für Festkörperchemie Universität Augsburg Universitätsstraße 1 86159 Augsburg Germany

3. Aylin Koldemir

   University of Münster

   Affiliation as printed

   Institut für Anorganische und Analytische Chemie Universität Münster Corrensstraße 30 48149 Münster Germany

4. Theresa Block

   University of Münster

   Affiliation as printed

   Institut für Anorganische und Analytische Chemie Universität Münster Corrensstraße 30 48149 Münster Germany

5. Rainer Pöttgen

   University of Münster

   Affiliation as printed

   Institut für Anorganische und Analytische Chemie Universität Münster Corrensstraße 30 48149 Münster Germany

6. Richard Dronskowski Aachen Institut für Anorganische Chemie

   RWTH Aachen University

   Affiliation as printed

   Institut für Anorganische Chemie RWTH Aachen University Landoltweg 1 52056 Aachen Germany

7. Henning A. Höppe corresponding

   University of Augsburg

   Affiliation as printed

   Lehrstuhl für Festkörperchemie Universität Augsburg Universitätsstraße 1 86159 Augsburg Germany