Ag[B(SO4)2] – Synthesis, Crystal Structure, and Characterization of the First Precious-Metal Borosulfate
Jörn Bruns
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
Search for more papers by this authorMaren Podewitz
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
Search for more papers by this authorMichael Schauperl
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
Search for more papers by this authorKlaus R. Liedl
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
Search for more papers by this authorOliver Janka
Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Correnstrasse 30, 48149 Münster, Germany
Search for more papers by this authorRainer Pöttgen
Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Correnstrasse 30, 48149 Münster, Germany
Search for more papers by this authorCorresponding Author
Hubert Huppertz
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
E-mail: [email protected]
https://www.uibk.ac.at/aatc/mitarbeiter/hub/
Search for more papers by this authorJörn Bruns
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
Search for more papers by this authorMaren Podewitz
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
Search for more papers by this authorMichael Schauperl
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
Search for more papers by this authorKlaus R. Liedl
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
Search for more papers by this authorOliver Janka
Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Correnstrasse 30, 48149 Münster, Germany
Search for more papers by this authorRainer Pöttgen
Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Correnstrasse 30, 48149 Münster, Germany
Search for more papers by this authorCorresponding Author
Hubert Huppertz
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
Institut für Allgemeine, Anorganische und Theoretische Chemie, Leopold-Franzens-Universität Innsbruck, Innrain 80–82, 6020 Innsbruck, Austria
E-mail: [email protected]
https://www.uibk.ac.at/aatc/mitarbeiter/hub/
Search for more papers by this authorGraphical Abstract
The first precious-metal borosulfate is obtained under harsh conditions. The reaction of Ag(NO3) with H3BO3 in oleum leads to Ag[B(SO4)2]. Single-crystal X-ray diffraction reveals tetragonal packing of AgI cations and infinite chains of [B(SO4)2]– anions. XRD, IR and Raman spectroscopic, and magnetochemical measurements were performed and further corroborated by means of quantum-chemical studies.
Abstract
The reaction of Ag(NO3) with H3BO3 in oleum (20 % SO3) yielded single crystals of Ag[B(SO4)2] [tetragonal, P4/ncc, Z = 4, a = 8.6679(5) Å, c = 7.2897(5) Å, V = 547.69(7) Å3]. In Ag[B(SO4)2], infinite anionic chains, according to the Niggli formula ∞1[B(SO4)4/2]–, are found in tetragonal-rod packing with charge compensation by AgI cations. The chains are built by central boron atoms coordinated through oxygen atoms to four bidentate bridging SO4 tetrahedra. Terminal oxygen atoms of the SO4 tetrahedra coordinate to the silver cations in the form of slightly distorted square prisms. Magnetochemical investigations reveal the expected closed-shell behavior of d10 cations. DFT investigations of the solid-state structure corroborate the experimental findings and permit the assignment of vibrational spectroscopic data.
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