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Preparation of Two Quantum‐Chemically Predicted, Isomeric [Br 4 F 13 ] – Anions in the Solid State
Author(s) -
Bandemehr Jascha,
Ivlev Sergei I.,
Karttunen Antti J.,
Kraus Florian
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000875
Subject(s) - chemistry , monoclinic crystal system , crystallography , molecule , raman spectroscopy , x ray crystallography , crystal structure , crystallization , infrared spectroscopy , solid state , quantum chemical , diffraction , organic chemistry , physics , optics
Two isomeric tridecafluoridotetrabromate(III) anions, [Br 4 F 13 ] – , both previously predicted by quantum‐chemical calculations, have serendipitously been obtained from the reaction of BrF 3 with BaF 2 . Single crystals of Ba 2 [Br 3 F 10 ] 2 [Br 4 F 13 ] 2 were selected from the reaction mixture at approximately 10 °C. The crystal structure contains two novel, isomeric [Br 4 F 13 ] – anions besides the known, star‐shaped [Br 3 F 10 ] – anions. It crystallized in the monoclinic space group P 1 n 1 (No. 7) with a = 8.8519(18), b = 15.217(3), c = 14.628(3) Å, β = 90.34(3)°, V = 1970.4(7) Å 3 and Z = 2, mP 124 at 100 K. The compound was additionally investigated using quantum‐chemical solid‐state calculations. If however crystals from the above reaction mixture were selected at room temperature, the compound Ba[Br 3 F 10 ] 2 · BrF 3 was obtained containing disordered BrF 3 molecules of crystallization besides [Br 3 F 10 ] – anions. The [Br 4 F 13 ] – molecules were no longer present. Ba[Br 3 F 10 ] 2 · BrF 3 crystallized in the cubic space group Pa 3 (No. 205) with a = 12.4903(14) Å, V = 1948.6(7) Å 3 , Z = 4, cP 124, T = 100 K. The much easier to handle latter compound was additionally investigated using powder X‐ray diffraction, as well as IR and Raman spectroscopy.