Résumé
Reactions between XeF2, MnF3 and UV-irradiated elemental F2 in anhydrous HF have yielded [XeF5]2[MnF6] and XeF5MnF5; meanwhile, [XeF5]4[Mn8F36] has been observed as a minor phase upon the crystallization of the product obtained by fluorination of an n(XeF2)/n(MnF3) = 1:3 mixture in the presence of an UV source. The crystal structure of [XeF5]2[MnF6] is isotypic with the known [XeF5]2[PdF6]. Its asymmetric structural unit consists of two crystallographically unique [XeF5]+ cations and a [MnF6]2– anion. The single-crystal structure determination of XeF6·2MnF4 reveals that it is better formulated as [XeF5]4[Mn8F36]. Discrete octameric [Mn8F36]4– anions are built from eight MnF6 octahedra, each sharing three vertices, in the shape of a ring, which is different from the previously known cubic [Ti8F36]4– anion. The main structural feature of the anionic part of the crystal structure of [XeF5][MnF5] (determined from both X-ray single-crystal and synchrotron X-ray powder diffraction data) is infinite zigzag chains of distorted MnF6 octahedra that share cis vertices. [XeF5][MnF5] is paramagnetic in the 296–200 K temperature range, with a Curie constant of C = 1.87 emu K mol–1 (µeff = 3.87 µB) and a Curie–Weiss temperature of θ = –9.3 K. Below 100 K, there is weak antiferromagnetic coupling between the MnIV ions, with a coupling constant of J = –1.3 cm–1. Raman spectra showed that [XeF5]2[MnF6] decomposes at ambient temperature in a He–Ne laser beam (power > 1.7 mW) to [XeF5][MnF5], with further decomposition to MnF3.
langue originale | Anglais |
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Pages (de - à) | 2130-2137 |
Nombre de pages | 8 |
journal | European Journal of Inorganic Chemistry |
Volume | 2017 |
Numéro de publication | 14 |
Les DOIs | |
Etat de la publication | Publié - 10 avr. 2017 |
Empreinte digitale
Examiner les sujets de recherche de « Photochemical Synthesis and Characterization of Xenon(VI) Hexafluoridomanganates(IV) ». Ensemble, ils forment une empreinte digitale unique.Ensembles de données
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CSD 1791492: Experimental Crystal Structure Determination
Mazej, Z. (Créateur), Goreshnik, E. (Créateur), Jaglicic, Z. (Contributeur), Filinchuk, Y. (Créateur), Tumanov, N. (Contributeur) & Akselrud, L. G. (Contributeur), University of Namur, 1 janv. 2017
DOI: 10.25505/fiz.icsd.cc1y462c, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc1y462c&sid=DataCite
Ensemble de données
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CSD 1791493: Experimental Crystal Structure Determination
Mazej, Z. (Créateur), Goreshnik, E. (Créateur), Jaglicic, Z. (Contributeur), Filinchuk, Y. (Créateur), Tumanov, N. (Contributeur) & Akselrud, L. G. (Contributeur), University of Namur, 1 janv. 2017
DOI: 10.25505/fiz.icsd.cc1y463d, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc1y463d&sid=DataCite
Ensemble de données
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CSD 1791491: Experimental Crystal Structure Determination
Mazej, Z. (Créateur), Goreshnik, E. (Créateur), Jaglicic, Z. (Contributeur), Filinchuk, Y. (Créateur), Tumanov, N. (Contributeur) & Akselrud, L. G. (Contributeur), University of Namur, 1 janv. 2017
DOI: 10.25505/fiz.icsd.cc1y461b, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc1y461b&sid=DataCite
Ensemble de données