Synthesis and characterization of barium hexafluoridoosmates

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Materials and Methods
General: All of the operations with the compounds were carried out in an atmosphere of dry and purified argon (Westfalen AG, Münster, Germany), so that a possible contact of the substance with moisture or air was minimized (O 2 < 1 ppm, H 2 O < 1 ppm).BrF 3 was synthesized by slowly passing gaseous fluorine through liquid bromine in an FEP U-tube reactor.Anhydrous HF was additionally dried by storing it over K 2 NiF 6 .BaF 2 and Os were used without additional purification.
were handled and indexed using the WinXPOW software (v3.07) [18].Le Bail profile fitting, space group assignment and Rietveld refinement were done in the Jana2006 software [19].The structure solution prior to the Rietveld refinement was done using the SUPERFLIP algorithm [20] implemented in Jana2006.Barium and osmium atoms were refined isotropic, whereas the displacement parameters of the fluorine atoms were fixed.
IR Spectroscopy: The IR spectra of BaOsF 6 were recorded using a Bruker Alpha FTIR spectrometer (Bruker Optik GmbH, Rosenheim, Germany) under an Ar atmosphere.The data were handled in the OPUS software package [21].
Computational Details: The structural and spectroscopic properties of Ba(OsF 6 ) 2 and BaOsF 6 were investigated using the CRYSTAL14 program package (CRYSTAL14) [22,23].Both the atomic positions and the lattice parameters were fully optimized using the PBE0 hybrid density functional method [24,25].Split-valence + polarization (SVP) level basis sets, as derived from the molecular Karlsruhe basis sets [26], were applied for all the atoms (see Supporting information for additional basis set details).The reciprocal space was sampled using a compound-dependent Monkhorst-Pack-type k-point grid: 6 × 4 × 2 for Ba(OsF 6 ) 2 and 8 × 8 × 8 for BaOsF 6 [27].For the evaluation of the Coulomb and exchange integrals (TOLINTEG), tight tolerance factors of 8, 8, 8, 8, and 16 were used.Default optimization convergence thresholds and DFT integration grids were applied in all calculations.For Ba(OsF 6 ) 2 , we carried out spin-polarized calculations.We set the spin orientations for the crystallographically inequivalent osmium atoms so that we obtained an antiferromagnetic ordering.The harmonic vibrational frequencies [28,29] and IR intensities [30] were obtained by using the computational schemes that were implemented in CRYSTAL.The IR spectrum of BaOsF 6 was broadened by using Lorenzian peak profile and FWHM of 8 cm −1 .

Synthesis of Barium Hexafluoridoosmate(V)
We used bromine trifluoride as the oxidizing and fluorinating medium for the synthesis of Ba(OsF 6 ) 2 [1].A stoichiometric mixture of BaF 2 and osmium metal was loaded into a vessel made of FEP (perfluorinated ethylene-propylene copolymer) and covered with an excess of BrF 3 .The tightly closed vessel was heated up to 120 • C and kept at this temperature for 24 h.Under these conditions, the oxidation of osmium slowly proceeds, according to the following Equation (1): 3 BaF 2 + 6 Os + 10 BrF 3 → 3 Ba(OsF 6 ) 2 + 5 Br 2 . ( After cooling down to room temperature the FEP vessel contained a clear green-brown solution.The excess of bromine trifluoride was pumped off yielding a fine pale-pink powder with a mass corresponding to the composition of Ba(OsF 6 ) 2 (see experimental details).

Synthesis of Barium Hexafluoridoosmate(IV)
BaOsF 6 was obtained by dissolving Ba(OsF 6 ) 2 in water and evaporating the solution at 80 • C. Upon the addition of water the solution became pale yellow and small gas bubbles appeared, which was reported to be OsO 4 [1].When the water was completely evaporated, a mixture of a black powder with colorless crystals was obtained.The nature of the black powder is yet unclear, however, the experimental data indicate that osmium(IV) dioxide formed due to the disproportionation of the OsF As no single crystals of barium hexafluoridoosmate(V) were obtained after evaporation of bromine trifluoride, we attempted to grow them using the following solvents: BrF 3 , HF, and H 2 O.However, in all of the cases, solvent molecules were retained in the crystal lattice forming solvates.

Bromine Trifluoride
If BrF 3 is not evaporated completely, the growth of large prismatic light-green crystals can be observed.The compound was identified as a BrF 3 solvate of Ba(OsF 6 ) 2 .However, we faced certain difficulties with the structure elucidation (see Section 3.3).Thus, details on this compound will be reported elsewhere.

Anhydrous Hydrogen Fluoride (aHF)
Ba(OsF 6 ) 2 was found to be well soluble in aHF forming a reddish solution and yielding pink crystals after evaporation.However, the resulting compound seems to retain at least one molecule of HF, and can be described with a preliminary formula "Ba(OsF 6 ) 2 •HF".

Water
It was noticed that during the synthesis of BaOsF 6 , the hydrolysis of Ba(OsF 6 ) 2 does not happen immediately.If water is quickly evaporated from a large surface of the solution without heating, the residue is a thin colorless film consisting of small crystals.According to single crystal diffraction data, they belong to another compound: Ba(OsF 6 ) 2 •6H 2 O.

Barium Hexafluoridoosmate(V)
No single crystals of Ba(OsF 6 ) 2 have been obtained so far.Despite that it was possible to successfully solve its crystal structure on the basis of powder X-ray diffraction data.The powder diffraction pattern of Ba(OsF 6 ) 2 recorded in a sealed quartz capillary is shown in Figure 1.The structure solution was carried out using the SUPERFLIP algorithm [31] and implemented in the Jana2006 software [32].Due to the instability of the Rietveld refinement only the Os and the Ba atoms could be refined isotropic.The thermal displacement parameters of the fluorine atoms had to be fixed.
All atoms in the crystal lattice of Ba(OsF 6 ) 2 occupy the general 4e Wyckoff position.The barium cation is coordinated by nine fluorine atoms belonging to nine different OsF 6 − anions resulting in a tricapped trigonal prismatic coordination sphere.Due to the low precision in the determination of the bond lengths and angles, it was not possible to carry out a detailed analysis of the structural features in Ba(OsF 6 ) 2 .For further information, we also optimized the structure with quantum chemical methods (DFT-PBE0/SVP level of theory).Some selected experimental and calculated values are given in Table 1, together with the corresponding values in KOsF 6 , which is a well characterized compound with the OsF 6 − anion [8].The experimental and theoretical lattice constants are in good agreement (differences less than 1.3%).The calculated bond lengths and angles correspond to the experimental values within the 3σ criterion.The crystallographic details of Ba(OsF 6 ) 2 are given in Table 2.We recorded the IR spectrum of Ba(OsF 6 ) 2 in the range from 4000 to circa 360 cm −1 .We observe no vibrations in the range down to 1500 cm −1 , which shows the purity of the compound.For further details of the band assignment in the region from 1500 to 360 cm −1 , see the Supporting Information, Figure S1 and Table S1.Additionally, we measured the 1 H and 19 F NMR spectra (Figure S2) of the compound dissolved in anhydrous hydrogen fluoride at room temperature.Due to the paramagnetic properties of osmium(V), the signals are broadened and the chemical shift is unpredictable in NMR spectroscopy [31].The paramagnetic shift of the solvent additionally gives information on the interaction of Ba(OsF 6 ) 2 with the solvent.
The proton signal of HF in the 1 H NMR spectrum of a Ba(OsF 6 ) 2 solution in anhydrous hydrogen fluoride (Figure 4) was observed at 19.93 ppm (ω 1/2 = 12.6 Hz).This is a downfield shift of 10.55 ppm when compared to neat anhydrous hydrogen fluoride which we observed at 8.38 ppm (ω 1/2 = 2.9 Hz).This trend is also observed in the 19 F NMR spectrum (Figure 5) where the fluorine signal of HF was observed at −176.32 ppm (ω 1/2 = 79.0Hz), which is a downfield shift of 22 ppm as compared to neat hydrogen fluoride (−198.32ppm, ω 1/2 = 12.0 Hz).This distinct paramagnetic down field shift is indicative for a considerable interaction of the paramagnetic OsF 6 − -moiety with the solvent, and it is expected if the osmium(V)-anion is in solution.The observed chemical shift of neat anhydrous hydrogen fluoride in the 1 H and 19 F NMR spectra are in good agreement with literature values [32].
Crystals 2018, 8, 11 7 of 13 details of the band assignment in the region from 1500 to 360 cm −1 , see the Supporting Information, Figure S1 and Table S1.Additionally, we measured the 1 H and 19 F NMR spectra (Figure S2) of the compound dissolved in anhydrous hydrogen fluoride at room temperature.Due to the paramagnetic properties of osmium(V), the signals are broadened and the chemical shift is unpredictable in NMR spectroscopy [31].The paramagnetic shift of the solvent additionally gives information on the interaction of Ba(OsF6)2 with the solvent.
The proton signal of HF in the 1 H NMR spectrum of a Ba(OsF6)2 solution in anhydrous hydrogen fluoride (Figure 4) was observed at 19.93 ppm (ω1/2 = 12.6 Hz).This is a downfield shift of 10.55 ppm when compared to neat anhydrous hydrogen fluoride which we observed at 8.38 ppm (ω1/2 = 2.9 Hz).This trend is also observed in the 19 F NMR spectrum (Figure 5) where the fluorine signal of HF was observed at −176.32 ppm (ω1/2 = 79.0Hz), which is a downfield shift of 22 ppm as compared to neat hydrogen fluoride (−198.32ppm, ω1/2 = 12.0 Hz).This distinct paramagnetic down field shift is indicative for a considerable interaction of the paramagnetic OsF6 − -moiety with the solvent, and it is expected if the osmium(V)-anion is in solution.The observed chemical shift of neat anhydrous hydrogen fluoride in the 1 H and 19 F NMR spectra are in good agreement with literature values [32].While in the 1 H NMR spectrum of Ba(OsF6)2 solutions in HF, no further signal was observed-as would be expected-one additional signal at 149.03 ppm, with a very broad line width (ω1/2 = 131.6Hz) was observed in the 19 F NMR spectrum (Figure 6).This signal is assigned to the OsF6 − -anion and indicates that only one species is present in solution.Therefore, the anions are solvent separated and do not interact with each other.details of the band assignment in the region from 1500 to 360 cm −1 , see the Supporting Information, Figure S1 and Table S1.
Additionally, we measured the 1 H and 19 F NMR spectra (Figure S2) of the compound dissolved in anhydrous hydrogen fluoride at room temperature.Due to the paramagnetic properties of osmium(V), the signals are broadened and the chemical shift is unpredictable in NMR spectroscopy [31].The paramagnetic shift of the solvent additionally gives information on the interaction of Ba(OsF6)2 with the solvent.
The proton signal of HF in the 1 H NMR spectrum of a Ba(OsF6)2 solution in anhydrous hydrogen fluoride (Figure 4) was observed at 19.93 ppm (ω1/2 = 12.6 Hz).This is a downfield shift of 10.55 ppm when compared to neat anhydrous hydrogen fluoride which we observed at 8.38 ppm (ω1/2 = 2.9 Hz).This trend is also observed in the 19 F NMR spectrum (Figure 5) where the fluorine signal of HF was observed at −176.32 ppm (ω1/2 = 79.0Hz), which is a downfield shift of 22 ppm as compared to neat hydrogen fluoride (−198.32ppm, ω1/2 = 12.0 Hz).This distinct paramagnetic down field shift is indicative for a considerable interaction of the paramagnetic OsF6 − -moiety with the solvent, and it is expected if the osmium(V)-anion is in solution.The observed chemical shift of neat anhydrous hydrogen fluoride in the 1 H and 19 F NMR spectra are in good agreement with literature values [32].While in the 1 H NMR spectrum of Ba(OsF6)2 solutions in HF, no further signal was observed-as would be expected-one additional signal at 149.03 ppm, with a very broad line width (ω1/2 = 131.6Hz) was observed in the 19 F NMR spectrum (Figure 6).This signal is assigned to the OsF6 − -anion and indicates that only one species is present in solution.Therefore, the anions are solvent separated and do not interact with each other.While in the 1 H NMR spectrum of Ba(OsF 6 ) 2 solutions in HF, no further signal was observed-as would be expected-one additional signal at 149.03 ppm, with a very broad line width (ω 1/2 = 131.6Hz) was observed in the 19 F NMR spectrum (Figure 6).This signal is assigned to the OsF 6 − -anion and indicates that only one species is present in solution.Therefore, the anions are solvent separated and do not interact with each other.

Barium Hexafluoridoosmate(IV)
As mentioned above, we obtained BaOsF6 in the form of colorless crystals with an impurity of the yet unidentified black powder.One of the crystals was selected under perfluorinated oil and was mounted on the goniometer using the MiTeGen MicroLoops TM system.

Barium Hexafluoridoosmate(IV)
As mentioned above, we obtained BaOsF 6 in the form of colorless crystals with an impurity of the yet unidentified black powder.One of the crystals was selected under perfluorinated oil and was mounted on the goniometer using the MiTeGen MicroLoops TM system.

Barium Hexafluoridoosmate(IV)
As mentioned above, we obtained BaOsF6 in the form of colorless crystals with an impurity of the yet unidentified black powder.One of the crystals was selected under perfluorinated oil and was mounted on the goniometer using the MiTeGen MicroLoops TM system.

Barium Hexafluoridoosmate(IV)
As mentioned above, we obtained BaOsF6 in the form of colorless crystals with an impurity of the yet unidentified black powder.One of the crystals was selected under perfluorinated oil and was mounted on the goniometer using the MiTeGen MicroLoops TM system.
By single crystal X-ray diffraction we observed that barium hexafluoridoosmate(IV) crystallizes in the trigonal centered space group type R3 (No. 148) with the cell parameters a = 7.3286 (10), c = 7.2658(15) Å, V = 337.95(12)Å 3 , Z = 3 at 100 K and, therefore, isotypic to BaRuF6 [8,33] and BaIrF6 [8,34].The crystal structure of BaOsF6 is shown in Figure 7.A section of its crystal structure showing one formula unit is given in Figure 8.Each osmium atom resides on the special 3a Wyckoff position (3) and is coordinated by six fluorine atoms (each on the general 18f position), resulting in an arrangement that is very similar to an octahedron (S 6 -symmetry).The Os-F bond length is 1.937(3) Å, the F-Os-F# angles are 85.68 (12), and 94.32 (12) • .Similar values are reported for the isotypic BaIrF 6 with the Ir-F bond being 1.936(4) Å and F-Ir-F# angles of 85.93 (17) and 94.07 (16) • .The experimentally determined and calculated cell parameters, bond lengths, and angles of BaOsF 6 are given in Table 2.As to the best of our knowledge, no other compound containing a OsF 6 2− anion has been structurally characterized so far, we compare distances and angles with the isotypic BaIrF 6 (Table 3).In order to identify the nature of the black powder that accompanies the formation of BaOsF 6 , we collected a powder X-ray diffraction pattern of the mixture.However, as it is seen from Figure 9, the pattern contains only the reflections of barium hexafluoridoosmate(IV), indicating an amorphous nature of the other phase.The barium ion occupies the special 3b Wyckoff position and is coordinated by twelve fluorine atoms, which stem from eight OsF6 2− anions.The resulting coordination polyhedron is close to a cuboctahedron.The Ba•••F distances are 2.773(3) and 2.870(3) Å.
Each osmium atom resides on the special 3a Wyckoff position (3 ) and is coordinated by six fluorine atoms (each on the general 18f position), resulting in an arrangement that is very similar to an octahedron (S6-symmetry).The Os-F bond length is 1.937(3) Å, the F-Os-F# angles are 85.68 (12), and 94.32 (12)°.Similar values are reported for the isotypic BaIrF6 with the Ir-F bond being 1.936(4) Å and F-Ir-F# angles of 85.93 (17) and 94.07( 16)°.The experimentally determined and calculated cell parameters, bond lengths, and angles of BaOsF6 are given in Table 2.As to the best of our knowledge, no other compound containing a OsF6 2− anion has been structurally characterized so far, we compare distances and angles with the isotypic BaIrF6 (Table 3).
In order to identify the nature of the black powder that accompanies the formation of BaOsF6, we collected a powder X-ray diffraction pattern of the mixture.However, as it is seen from Figure 9, the pattern contains only the reflections of barium hexafluoridoosmate(IV), indicating an amorphous nature of the other phase.An additional investigation by means of IR spectroscopy (Figure 10) did not show the presence of any characteristic vibrational modes, e.g., of the OH − group, indicating that the black powder is a relatively simple compound.The investigations on the identification of this phase are ongoing.An additional investigation by means of IR spectroscopy (Figure 10) did not show the presence of any characteristic vibrational modes, e.g., of the OH − group, indicating that the black powder is a relatively simple compound.The investigations on the identification of this phase are ongoing.Currently, we think that the phase may be osmium dioxide (see Reaction 2), which is known to be formed in amorphous state from the reduction of aqueous solutions of OsO 4 [35].Currently, we think that the phase may be osmium (see Reaction 2), which is known to be formed in amorphous state from the reduction of aqueous solutions of OsO4 [35].Unfortunately, the compound is insoluble in anhydrous HF, so no solution NMR spectrum could be obtained.

A barium Hexafluoridoosmate(V) Solvate of BrF3
In an attempt to grow single crystals of Ba(OsF6)2, we tried to use bromine trifluoride as a solvent.Upon partial evaporation of BrF3 and the subsequent cooling of the resulting solution down to room temperature, big pale-green prismatic crystals were obtained.One crystal was selected under perfluorinated oil using a polarizing light-optical microscope and mounted on the goniometer.
The obtained compound crystallizes in a primitive monoclinic cell with the cell parameters a = 15.539(3),b = 37.029 (7), c = 15.722(3)Å, β = 90.10(3)°,and V = 9046(3) Å 3 at 100 K.The tentative space group type is P21/n (No. 14).The structure solution and refinement did not lead to a chemically plausible model.Due to the β-angle being so close to 90°, we also attempted structure solutions in the orthorhombic crystal system and then using various twin refinements.However, the structure models obtained were not satisfactory.The refinement of the structure in one of the maximal translationengleiche subgroups of P21/n, namely Pn, P21, and P1 , led to no substantial improvement of the structural model.The investigations on the crystal structure of this solvate are ongoing and the results will be reported elsewhere.

A Barium Hexafluoridoosmate(V) Solvate of Hydrogen Fluoride
Anhydrous hydrogen fluoride (aHF) was used as the next solvent to obtain single crystals of Ba(OsF6)2.Upon dissolving Ba(OsF6)2 in aHF, a clear red solution was obtained.When the solvent was partially evaporated, red-pink crystals were formed.The crystals were selected directly out of aHF and mounted under perfluorinated oil.After solving the crystal structure, we identified this new compound preliminary as "Ba(OsF6)2•HF".
Barium bis(hexafluoridoosmate(V))-hydrogen fluoride (1/1) crystallizes in the orthorhombic crystal system.First, we obtained the lattice parameters a = 10.9127(12), b = 11.5853(11), and c = 15.900(2)Å, V = 2010.2(4)Å 3 at 100 K, and the space group type Pbcn (No. 60) was established.However, the structure model showed rather large displacement parameters for the fluorine ligands bound to the Os atom.As we could not resolve the disorder, we checked the reciprocal space for additional information and observed statistically significant superstructure reflections leading to the lattice parameters a = 21.8173(7), b = 31.7637(15), c = 11.8742(3)Å, and V = 8020.9(4)Å 3 at 100 K.However, all of our refinements in the larger unit cell led to unsatisfactory results.Currently, the crystal structure of the compound is still under investigation and will be reported elsewhere.Unfortunately, the compound is insoluble in anhydrous HF, so no solution NMR spectrum could be obtained.

A barium Hexafluoridoosmate(V) Solvate of BrF 3
In an to grow single crystals of Ba(OsF 6 ) 2 , we tried to use bromine trifluoride as a solvent.Upon partial evaporation of BrF 3 and the subsequent cooling of the resulting solution down to room temperature, big pale-green prismatic crystals were obtained.One crystal was selected under perfluorinated oil using a polarizing light-optical microscope and mounted on the goniometer.
The obtained compound crystallizes in a primitive monoclinic cell with the cell parameters a = 15.539(3),b = 37.029 (7), c = 15.722(3)Å, β = 90.10(3)• , and V = 9046(3) Å 3 at 100 K.The tentative space group type is P2 1 /n (No. 14).The structure solution and refinement did not lead to a chemically plausible model.Due to the β-angle being so close to 90 • , we also attempted structure solutions in the orthorhombic crystal system and then using various twin refinements.However, the structure models obtained were not satisfactory.The refinement of the structure in one of the maximal translationengleiche subgroups of P2 1 /n, namely Pn, P2 1 , and P1, led to no substantial improvement of the structural model.The investigations on the crystal structure of this solvate are ongoing and the results will be reported elsewhere.

A Barium Hexafluoridoosmate(V) Solvate of Hydrogen Fluoride
Anhydrous hydrogen fluoride (aHF) was used as the next solvent to obtain single crystals of Ba(OsF 6 ) 2 .Upon dissolving Ba(OsF 6 ) 2 in aHF, a clear red solution was obtained.When the solvent was partially evaporated, red-pink crystals were formed.The crystals were selected directly out of aHF and mounted under perfluorinated oil.After solving the crystal structure, we identified this new compound preliminary as "Ba(OsF 6 ) 2 •HF".
Barium bis(hexafluoridoosmate(V))-hydrogen fluoride (1/1) crystallizes in the orthorhombic crystal system.First, we obtained the lattice parameters a = 10.9127(12), b = 11.5853(11), and c = 15.900(2)Å, V = 2010.2(4)Å 3 at 100 K, and the space group type Pbcn (No. 60) was established.However, the structure model showed rather large displacement parameters for the fluorine ligands bound to the Os atom.As we could not resolve the disorder, we checked the reciprocal space for additional information and observed statistically significant superstructure reflections leading to

Barium Hexafluoridoosmate(V) Hexahydrate
We used water as the last choice of solvents in this study.Despite that Ba(OsF6)2 is hydrolyzed in water, this process is not instantaneous giving the chance to recrystallize the substance.However, the obtained crystals belong to another new compound: barium hexafluoridoosmate(V) hexahydrate, Ba(OsF6)2•6H2O.

Conclusions
In this work, we have synthesized and structurally characterized for the first time two alkaline-earth metal hexafluoridoosmates: Ba(OsF 6 ) 2 and BaOsF 6 .The compounds contain spatially isolated OsF 6 − (or OsF 6 2− respectively) anions with their symmetry close to O h .In an attempt to grow single crystals of Ba(OsF 6 ) 2 , we obtained three new solvates depending on the used solvent: Ba(OsF 6 )

Figure 2 .
Figure 2. The crystal structure of Ba(OsF6)2 (projection along a-axis).Atoms are shown with isotropic displacement parameters, F atoms with fixed ones.

Figure 3 .
Figure 3. Asymmetric unit of Ba(OsF6)2.Atoms are shown with isotropic displacement parameters, F atoms with fixed ones.

Figure 2 .
Figure 2. The crystal structure of Ba(OsF6)2 (projection along a-axis).Atoms are shown with isotropic displacement parameters, F atoms with fixed ones.

Figure 3 .
Figure 3. Asymmetric unit of Ba(OsF6)2.Atoms are shown with isotropic displacement parameters, F atoms with fixed ones.

Figure 2 .of 13 Figure 1 .
Figure 2. The crystal structure of Ba(OsF 6 ) 2 (projection along a-axis).Atoms are shown with isotropic displacement parameters, F atoms with fixed ones.

Figure 2 .
Figure 2. The crystal structure of Ba(OsF6)2 (projection along a-axis).Atoms are shown with isotropic displacement parameters, F atoms with fixed ones.

Figure 3 .
Figure 3. Asymmetric unit of Ba(OsF6)2.Atoms are shown with isotropic displacement parameters, F atoms with fixed ones.

Figure 3 .
Figure 3. Asymmetric unit of Ba(OsF 6 ) 2 .Atoms are shown with isotropic displacement parameters, F atoms with fixed ones.

Figure 6 .
Figure 6.A part of 19 F NMR spectrum of Ba(OsF6)2 in anhydrous HF showing the OsF6 − signal.

Figure 7 .
Figure 7.The crystal structure of BaOsF6 (projection along c-axis).Displacement ellipsoids are shown at 70% probability level at 100 K.

Figure 6 .
Figure 6.A part of 19 F NMR spectrum of Ba(OsF 6 ) 2 in anhydrous HF showing the OsF 6 − signal.

Figure 7 .
Figure 7.The crystal structure of BaOsF6 (projection along c-axis).Displacement ellipsoids are shown at 70% probability level at 100 K.

Figure 7 .
Figure 7.The crystal structure of BaOsF6 (projection along c-axis).Displacement ellipsoids are shown at 70% probability level at 100 K.

Figure 9 .
Figure 9. Powder X-ray diffraction pattern (at 293 K) of BaOsF6: the experimental data (black crosses), the Le Bail profile (red), and the differential profile (bottom, black).The calculated reflection positions for BaOsF6 are shown as black ticks.Rp = 0.0189, wRp = 0.0264.

Figure 9 .
Figure 9. Powder X-ray diffraction pattern (at 293 K) of BaOsF 6 : the experimental data (black crosses), the Le Bail profile (red), and the differential profile (bottom, black).The calculated reflection positions for BaOsF 6 are shown as black ticks.R p = 0.0189, wR p = 0.0264.

Figure 11 .
Figure 11.The crystal structure of Ba(OsF6)2•6H2O (projection along c-axis).Displacement ellipsoids are shown at 70% probability level at 100 K.All the non-hydrogen atoms are shown anisotropic, hydrogen atoms are shown with arbitrary radii.

Figure 12 .
Figure 12.Fragment of the crystal structure of Ba(OsF6)2•6H2O showing the coordination of OsF6 − and H2O around Ba 2+ .Displacement ellipsoids are shown at 70% probability level at 100 K.All non-hydrogen atoms are shown anisotropic, hydrogen atoms are shown with arbitrary radii.

Figure 11 .
Figure 11.The crystal structure of Ba(OsF 6 ) 2 •6H 2 O (projection along c-axis).Displacement ellipsoids are shown at 70% probability level at 100 K.All the non-hydrogen atoms are shown anisotropic, hydrogen atoms are shown with arbitrary radii.

Figure 11 .
Figure 11.The crystal structure of Ba(OsF6)2•6H2O (projection along c-axis).Displacement ellipsoids are shown at 70% probability level at 100 K.All the non-hydrogen atoms are shown anisotropic, hydrogen atoms are shown with arbitrary radii.

Figure 12 .
Figure 12.Fragment of the crystal structure of Ba(OsF6)2•6H2O showing the coordination of OsF6 − and H2O around Ba 2+ .Displacement ellipsoids are shown at 70% probability level at 100 K.All non-hydrogen atoms are shown anisotropic, hydrogen atoms are shown with arbitrary radii.

Figure 12 .
Figure 12.Fragment of the crystal structure of Ba(OsF 6 ) 2 •6H 2 O showing the coordination of OsF 6 − and H 2 O around Ba 2+ .Displacement ellipsoids are shown at 70% probability level at 100 K.All non-hydrogen atoms are shown anisotropic, hydrogen atoms are shown with arbitrary radii.
6− anion in aqueous solution.The tentative reaction can be described by the following
* Minimal and maximal values for distances and angles are given.F# denotes another fluorine atom in equivalent to F.

Table 2 .
Crystallographic details of the characterized compounds.
Supplementary Materials: