Reactions of Manganese(II) Fluoride in the Superacidic Systems HF/SbF5 and HF/GeF4 - Crystal Structure of Mn(SbF6)2 and Vibrational Spectra of MnGeF6

Abstract

Mn(SbF 6 ) 2 was prepared from MnF 2 and SbF 5 in aHF (anhydrous HF) and single crystals were obtained from the respective solution. The compound crystallises in the triclinic space group P 1 (No. 2) with a = 517.3(2) pm, b = 554.9(2) pm, c = 888.2(2) pm, a = 73.98(3)°, b = 89.17(2)°, c = 62.54(2)°and Z = 1. MnGeF 6 was prepared from MnF 2 and GeF 4 in aHF and by metathetical reaction between solutions of K 2 GeF 6 in aHF and Mn(AsF 6 ) 2 in aHF. Attempt to isolate Mn(GeF 5 ) 2 prepared by metathetical reaction between solutions of XeF 5 GeF 5 in aHF and Mn(AsF 6 ) 2 in aHF failed, although some slight evidences for its existence were obtained. Vibrational data of MnGeF 6 are in agreement with lowering of the symmetry of GeF 6 2± from O h to C 3i because of the site symmetry effects.

X-ray single crystal structures of Hg(AuF6)2 and AgFAuF6

“…The known compounds with general formula M II (X V F 6 ) 2 adopt one of the four structural types [1,4,5]. The first and most common structural type is the Ni(SbF 6 ) 2 -type [4] (Fig.…”

“…1. (a) Packing of slabs in Mn(SbF 6 ) 2 (view along a-axis) [5] (example of the Ni(SbF 6 ) 2 -structural type) and (b) three-dimensional framework in Cd(AuF 6 ) 2 (view along baxis) [2]. Orange octahedra (dark) represent X V F 6 (X = Sb, Au) units.…”

Recent achievements in the synthesis and characterization of metal hexafluorantimonates and hexafluoroaurates

“…The previously reported X-ray single crystal analyses and the X-ray powder diffraction patterns indicate that three structural types are adopted by most of the known compounds with general formula M II (X V F 6 ) 2 (Table 7) [4,5,9,17,18,[28][29][30][31][32][33][34][35][36].…”

“…The vibrational spectra of M(SbF 6 ) 2 (M = Cr, Mn, Fe, Co, Ni, Cu, Pd, Ag) confirm strong interactions between cation and anion via fluorine bridging, consistent with the highly distorted SbF 6 octahedra found in the known single crystal structures of M(SbF 6 ) 2 (M = Mn [17], Ag [4] and Pd [18]) compounds. The small differences in the X-ray powder patterns of the divalent transition metal hexafluoroantimonates (Table 3) are probably the consequence, not only of slight differences in their crystal structures, but of the fact that metal(II) hexafluorantimonates, when isolated from aHF solution, are usually of low crystallinity and consequently yield very poor X-ray powder diffraction patterns.…”

“…10 a Up to date the crystal structures of M(SbF 6 ) 2 (M = Ag: triclinic, P1, with a = 522.4(1) pm, b = 546.7(2) pm, c = 877.9(2) pm, a = 75.78(2)8, b = 89.02(2)8, g = 62.29(2)8 and z = 1 [4]; Pd: triclinic, P1 with a = 884.3 pm, b = 557.5 pm, c = 512.3 pm, a = 117.38, b = 89.88, g = 105.58 and z = 1 [18]; Mn: triclinic, P1, with a = 517.3(2) pm, b = 554.9(2) pm, c = 888.2(2) pm, a = 73.98(3)8, b = 89.17(2)8, g = 62.54(2)8 and z = 1[17]) have been determined using single crystal data. b Ref [5]…”