research communications
The `super acid' BF3H2O stabilized by 1,4-dioxane: new preparative aspects and the of BF3H2O·C4H8O2
aInstitut für Anorganische Chemie und Strukturchemie, Lehrstuhl II: Material- und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany
*Correspondence e-mail: peter.barthen@hhu.de, wfrank@hhu.de
Highly Brønsted-acidic boron trifluoride monohydrate, a widely used `super acid-catalyst', is a colourless fuming liquid that releases BF3 at room temperature. Compared to the liquid components, i.e. boron trifluoride monohydrate and 1,4-dioxane, their 1:1 adduct, BF3H2O·C4H8O2, is a solid with pronounced thermal stability (m.p. 401–403 K). The of the long-time-stable easy-to-handle and weighable compound is reported along with new preparative aspects and the results of 1H, 11B, 13C and 19F spectroscopic investigations, particularly documenting its high Brønsted acidity in acetonitrile solution. The remarkable stability of solid BF3H2O·C4H8O2 is attributed to the chain structure established by O—H⋯O hydrogen bonds of exceptional strength {O2⋯H1—O1 [O⋯O = 2.534 (3) Å] and O1—H1⋯O3i [2.539 (3) Å] in the concatenating unit >O2⋯H1—O1—H2⋯O3i<}, taking into account the molecular (non-ionic) character of the structural moieties. Indirectly, this structural feature documents the outstanding acidification of the H2O molecule bound to BF3 and reflects the super acid nature of BF3H2O. In detail, the C22(7) zigzag chain system of hydrogen bonding in the title structure is characterized by the double hydrogen-bond donor and double (κO,κO′) hydrogen-bond acceptor functionality of the aqua ligand and dioxane molecule, respectively, the almost equal strength of both hydrogen bonds, the approximatety linear arrangement of the dioxane O atoms and the two neighbouring water O atoms. Furthermore, the approximately planar arrangement of B, F and O atoms in sheets perpendicular to the c axis of the orthorhombic is a characteristic structural feature.
1. Chemical context
Solutions of boron trifluoride in water have been under investigation for more than 200 years (Gay-Lussac & Thenard, 1809; Davy, 1812; Berzelius, 1824). Meerwein (1933) was able to isolate the BF3 dihydrate and, after addition of one further equivalent of BF3 at low temperature, the BF3 monohydrate also. Both hydrates were examined in detail (Klinkenberg & Ketelaar, 1935; McGrath et al., 1944; Greenwood & Martin, 1951; Wamser, 1951; Pawlenko, 1959) and while the dihydrate was shown to be distillable without decomposition under reduced pressure, boron trifluoride monohydrate releases BF3 above its melting point of 279.2 K. At room temperature, it is a colourless fuming liquid with a density of 1.8 g ml−1. To examine the acidity of the monohydrate, reactions with and carboxylic acids etc. were performed by Meerwein & Pannwitz (1934). They obtained BF3H2O·C4H8O2, which they called the dioxane salt of boron trifluoride monohydrate, by adding BF3H2O to a solution of 1,4-dioxane in petroleum naphta. BF3H2O·C4H8O2 (1) precipitates as needle-shaped crystals which melt at 401–403 K with decomposition (Meerwein & Pannwitz, 1934). Unexpectedly, the experiment described in §6 resulted in the same product. The primordial idea of this experiment was to prepare an anhydrous solution of HBF4 from HBF4/H2O (1:1 w:w) by distilling off water as the 1,4-dioxane/water azeotrope with coincident replacement of water by an excess of 1,4-dioxane. The dioxane adduct 1 starts to precipitate after a short period of time if a small amount of water remains in the resulting liquid. The formation of 1 in a `HBF4 solution' impressively illustrates how efficently BF3 is stabilized by water and dioxane. The reactions and equilibria of HBF4-, BF3-, H2O- and HF-containing systems have been examined in detail (Pawlenko, 1968; Gascard & Mascherpa, 1973; Christe et al., 1975; Mootz & Steffen, 1981a; Yeo & Ford, 2006; Dubey et al., 2007) and it remains amazing that BF3H2O, unlike the other boron trihalide/water mixtures, releases the strong Lewis-acid (BF3) unhydrolysed. Investigations by Greenwood & Martin (1951) showed that BF3H2O is highly ionized in the liquid state and that the Hammett acidity of H[BF3OH] is H0 = −11.4. By NMR spectroscopic determination of the thermodynamic from 13C chemical-shift changes of the signals of unsaturated at infinite dilution in the acid under investigation, Farcasui & Ghenciu (1992) found boron trifluoride monohydrate to be super acidic, with H0 < −14. The applications of this super acid are numerous, e.g. as a highly effective catalyst for several Friedel–Craft reactions (Yoneda et al., 1969; Oyama et al., 1978; Liu et al., 2003; Prakash et al., 2016, and references therein). The long-time-stable and easy-to-handle solid 1 provides the `super acid BF3H2O' in a safe and efficient way.
Although Meerwein & Pannwitz (1934) isolated compound 1 (m.p. 401–403 K) and a solid, in which BF3H2O is stabilized by 1,8-cineole (m.p. 344–346 K) more than 80 years ago, the crystal structures of these compounds are still unknown and the reasons for the unexpected high thermal stability, especially of the dioxane adduct, are still unknown. Generally, there are very rare examples of crystal structures with BF3H2O moieties bound to O-donor molecules. The of boron trifluoride monohydrate itself has been reported by Mootz & Steffen (1981b), after redetermination of the of the dihydrate in the same year (Mootz & Steffen, 1981c; Bang & Carpenter, 1964). Stabilization of the mono- and dihydrate with 18-crown-6 (Bott et al., 1991; Feinberg et al., 1993; Simonov et al., 1995) or of BF3H2O with dicyclohexane-18-crown-6 (Fonar et al., 1997) led to three further crystal structures containing the BF3H2O moiety and, as the most recent example, stabilization with triphenylphosphane oxide (Chekhlov, 2005) gave a crystalline 1:2 adduct of BF3H2O and (C6H5)3PO.
2. Structural commentary
Compound 1 was found to crystallize in the orthorhombic Pbca with eight formula units in the and all components in general positions. Fig. 1 shows the of the which contains aquatrifluoridoboron and 1,4-dioxane molecular moieties. The dioxane moiety is free of any kind of often recognized in the case of saturated six-membered ring species. Bond lengths, angles and torsion angles defining the chair conformation are in excellent agreement with the expectations for a `fully ordered' dioxane molecule, e.g. found in the structure of uncomplexed 1,4-dioxane at 153 K (Buschmann et al., 1986). Compared to the mean equivalent isotropic displacement parameter (Ueq) of the C and O atoms in the 1,4-dioxane moiety [= 0.0427 (6) Å2], the mean Ueq value of B1, O1 and F1 to F3 in the aquatrifluoridoboron moiety [0.0867 (8) Å2] is dramatically higher and correction for libration is needed prior to comparison with the geometries of BF3H2O moieties in related compounds. In Table 1, the uncorrected and corrected (Schomaker & Trueblood, 1968; RG = 0.0241) B—O and B—F bond lengths of 1 are given in comparison to the bond lengths of BF3H2O (Mootz & Steffen, 1981c) and BF3H2O·H2O (Mootz & Steffen, 1981b). After correction, the values of 1 agree well with those of the hydrates and those in almost undistorted BF4− as found in Li[BF4] at 200 K [1.387 (3)–1.391 (3) Å; Matsumoto et al., 2006] or in H5O2[BF4] [1.381 (2)–1.399 (2) Å; Mootz & Steffen, 1981a]. The bond-valence sum of B1 is as expected taking into account the `uncorrected' nature of the r0 values used (Brown & Altermatt, 1985). Interestingly, for all compounds mentioned in Table 1, the B—F bond perpendicular to the plane of the aqua ligand (1: B1—F3; BF3H2O: B1—F2; BF3H2O·H2O: B1—F3) is slightly but significantly longer than the other two B—F bonds, probably attributable to a small destabilizing interaction with the oxygen lone pair. The F—B—O angles in all three compounds [1: 105.6 (3)–109.8 (3)°; BF3H2O: 105.9 (4)–108.1 (4)°; BF3H2O·H2O: 106.3 (1)–109.8 (1)°] are smaller than the F—B—F angles [1: 109.9 (3)–112.1 (3)°; BF3H2O: 111.2 (4)–113.0 (4)°; BF3H2O·H2O: 109.8 (1)–114.0 (1)°]. This fits to the observation (Table 1) that the B—O bond in the BF3H2O moiety is relatively weaker than the B—F bonds and the planar geometry of BF3 is preserved in the aqua complex to some extent. Furthermore, for all three compounds, the O—B—F angle including the F atom that is approximately in plane with the aqua ligand [1: O1—B1—F1 = 105.6 (3)°; BF3H2O: O—B—F3 = 105.9 (4)°; BF3H2O·H2O: O1—B—F2 = 106.3 (1)°] is significantly smaller than the other O—B—F angles. This observation may be attributed to an attractive F⋯H interaction within the moiety.
Although both BF3H2O and 1,4-dioxane are liquids at room temperature, adduct 1 is a solid with a remarkably high melting point (401–403 K), mainly resulting from the concatenation of the molecular components via O—H⋯O hydrogen bonding, as shown in Fig. 2. The high stability might be correlated to the exceptional strength of both O2⋯H1—O1 [O⋯O = 2.534 (3) Å] and O1—H1⋯O3i [2.539 (3) Å] in the concatenating >O2⋯H1—O1—H2⋯O3i< unit. Indirectly, this structural feature documents the outstanding acidification of the H2O molecule bound to BF3 and reflects the super acid nature of BF3H2O. Further details of the hydrogen bonding are given in Table 2. To the best of our knowledge, there is no example of a water ligand bonded to a nonmetal or a metal with the ligand engaged in a hydrogen bond of similar strength (O⋯O < 2.60 Å) to an O atom of a dioxane molecule. In the adduct 18-crown-6·BF3H2O (m.p. 345 K), mentioned in §1, the aqua ligand is hydrogen bonded to two O-donor atoms and the O⋯O distances are 2.76 and 2.80 Å (Feinberg et al., 1993). In the structure of BF3H2O·H2O, the nonligating water molecule plays a similar role as bridging species as the dioxane molecule in 1. The O⋯O distances in the characteristic ⋯H—O—H⋯O(H2)⋯H—O—H⋯ unit are 2.631 and 2.643 Å (Mootz & Steffen, 1981c), i.e. as compared to the very strong Brønsted acids fluorosulfuric acid [O⋯O = 2.643 (1) Å] or trifluoromethanesulfonic acid [O⋯O = 2.640 (4) Å] (Bartmann & Mootz, 1990), for example, the hydrogen bonding is of the same strength in the dihydrate and much stronger in the adduct 1.
3. Supramolecular features
As mentioned before, in the solid of 1 the aqua ligand of the BF3H2O moiety acts as a hydrogen-bond donor in two directions, establishing a C22(7) graph set (Etter, 1990) (Fig. 2). The propagation vector of the zigzag chain is parallel to the b axis of the Note the almost equal strength of both hydrogen bonds. Fig. 3 shows the arrangement of the chains in the solid due to van der Waals interactions.
4. Database survey
A search of the Cambridge Structural Database (CSD; Version 5.40, November 2018 update; Groom et al., 2016) for the BF3H2O moiety yielded six structures: the crown ether adducts 18-crown-6 monoaquatrifluoridoboron toluene semisolvate (CSD refcode SIXFOU; Bott et al. 1991), 18-crown-6 bis(monoaquatrifluoridoboron) dihydrate (LEKYIJ; Feinberg et al. 1993, Simonov et al., 1995) and dicyclohexano-18-crown-6 bis(monoaquatrifluoridoboron) (NIYGAD; Fonar et al., 1997); the phosphane oxide adduct monoaquatrifluoridoboron bis(triphenylphosphane oxide) (XATWAR; Chekhlov, 2005); two transition-metal coordination compounds [CIGVUJ10 (Van Rijn et al., 1987) and UKAJIA (Orain et al., 2010)], containing cocrystallized monoaquatrifluoridoboron moieties. As mentioned above, in addition to these reports on compounds having organic components, there is the report of Mootz & Steffen (1981b) on the inorganic parent compound BF3H2O and there are two reports on the dihydrate BF3H2O·H2O (Mootz & Steffen, 1981c; Bang & Carpenter, 1964).
5. NMR spectroscopy
NMR studies of BF3H2O·C4H8O2 have not been published so far. Ford & Richards (1956) have shown by low-temperature NMR investigations that, in the solid state, BF3H2O and BF3H2O·H2O are not ionized. Diehl (1958) reported the 19F NMR spectra of BF3H2O in aqueous solution. He observed separate broad resonances which he attributed to HBF3OH, HBF4, HBF2(OH)2 and HBF(OH)3 in concentrated solutions at 243 K with coalescence of the peaks at higher temperatures. Gillespie & Hartman (1967) have shown by low-temperature (193 K) 1H and 19F NMR spetroscopy that BF3H2O is formed in dilute solutions in acetone containing both water and BF3. They found two major peaks in the 19F NMR spectrum and assigned the low-field peak (−146.05 ppm) to the 1:1 complex of BF3 with acetone and the high-field peak (−146.59 ppm) to BF3H2O in acetone. The corresponding 1H NMR signals were detected by Gillespie & Hartmann at 12.42 ppm as multipletts. In our experiments, in the presence of CD3CN and 1,4-dioxane and at a significantly higher temperature (297 K), the protons were detected as a broad singlet at 9.41 ppm. Gottlieb et al. (1997) indicated that the influence of temperature on the NMR shift overcompensates the influence of the solvent if the basicity of the solvents is similar. Apart from this effect, the high acidity of the oxygen-bonded 1H nuclei in the title compound is depicted by a shift of more than 7 ppm to higher frequencies (H2O in CD3CN: s, 2.13 ppm; Fulmer et al. 2010). The chemical shifts of the NMR signals belonging to 1,4-dioxane are close to those of the uncomplexed compound (C4H8O2 in CD3CN: 1H: s, 3.60 ppm; 13C: 68.5 ppm; Fulmer et al., 2010). Due to the comparable donor numbers (Gutmann, 1976) of acetonitrile (NMR solvent) and 1,4-dioxane, it can be concluded that the acidity of BF3H2O is not critically reduced by 1,4-dioxane with respect to its application as a super acid-catalyst.
The NMR sample was investigated in a 5 mm precision glass NMR tube (Wilmad 507) at 297 K in the deuterium-locked mode on a Bruker Avance III 400 MHz spectrometer operating at 400.17, 376.54, 128.23 or 100.62 MHz for 1H, 19F, 11B and 13C nuclei, respectively. The 1H NMR and 13C chemical shifts were referenced with respect to tetramethylsilane yielding the for CD3CN (contains CD2HCN) as 1.96 ppm and CD3CN as 118.7 ppm. The 19F chemical shifts were referenced with respect to CFCl3 (0 ppm) as The 11B chemical shifts were referenced with respect to BF3·(C2H5)2O (0 ppm) as 68 mg of ground crystals were dissolved in 0.5 ml CD3CN to prepare the NMR sample: 1H NMR: 3.71 (s, 8H, C4H8O2), 9.41 (s, 2H, H2O). 19F NMR: −148.10 (s, 11BF3), −148.04 (s, 10BF3). 11B NMR: −0.1 (s, 11BF3). 13C NMR: 68.0 [t, 1J(C,H) = 189 Hz, C4H8O2].
6. Synthesis and crystallization
All preparations and sample manipulations were carried out in tetrafluoroethylene hexafluoropropylene 3OH]− by 19F NMR spectroscopy. Depending on the quantity of these anions, hydrofluoric acid (48 wt% in water, Sigma–Aldrich) was added. In a typical experiment, to 131.4 g (1.24 mol) of HBF4/H2O, 4.53 g (0.11 mol) HF/H2O was added at 273 K. The mixture was stirred for 15 min, before 430 g of 1,4-dioxane was added at the same temperature. Subsequently, the reaction mixture was heated and the 1,4-dioxane–water azeotrope was distilled off under normal pressure until the boiling point (361 K) began to change. 368 g of azeotrope was removed by the distillation and the residue was a pale-brown solution. This solution was stored in a sealed FEP flask under an atmosphere of dry argon (Argon 5.0). After 1 h, the formation of colourless crystals of 1 started and was allowed to continue for 9 d. The crystals were isolated under an argon atmosphere and washed with hexane/1,4-dioxane (10:1 v/v) three times using Schlenk techniques. 40.7 g (0.23 mol) were collected after drying the almost hexagonal colourless crystals in an argon stream (40 min). Compound 1 is stable at room temperature and shows a poor solubility in 1,4-dioxane, but a good solubility in acetonitrile.
(FEP) vessels. Tetrafluoroboric acid solution (50 wt% in water; Fluka Chemicals) was probed for its content of [BFAn elemental analysis was performed with a HEKATECH EA 3000 elemental analyser using Callidus 2E3 software. 1.7 mg of freshly ground crystals were used and a modifier was added to suppress the influence of the high fluorine content. Analysis calculated (%) for C4H10BF3O3: 27.62 C, 5.80 H; found: 27.84 C, 5.87 H.
7. Refinement
Crystal data, data collection and structure . The positions of all H atoms were identified via subsequent ΔF syntheses. In the a riding model was applied, using idealized C—H bond lengths, as well as H—C—H and C—C—H angles. The Uiso values were set at 1.2Ueq(C) for methylene H atoms. For the H atoms of the aqua ligand, positional parameters and Uiso values were refined.
details are summarized in Table 3
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Supporting information
https://doi.org/10.1107/S2056989019014312/eb2021sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019014312/eb2021Isup2.hkl
Data collection: X-AREA (Stoe & Cie, 2009); cell
X-AREA (Stoe & Cie, 2009); data reduction: X-AREA (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).H2BF3O·C4H8O2 | Dx = 1.527 Mg m−3 |
Mr = 173.93 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 7579 reflections |
a = 7.6835 (5) Å | θ = 2.7–25.9° |
b = 12.929 (1) Å | µ = 0.16 mm−1 |
c = 15.2326 (13) Å | T = 223 K |
V = 1513.2 (2) Å3 | Prisms, colourless |
Z = 8 | 0.69 × 0.48 × 0.42 mm |
F(000) = 720 |
Stoe IPDS diffractometer | 932 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.085 |
φ–scan | θmax = 26.0°, θmin = 2.7° |
Absorption correction: multi-scan (Blessing, 1989) | h = −9→9 |
Tmin = 0.673, Tmax = 0.920 | k = −15→15 |
19913 measured reflections | l = −18→18 |
1481 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.067 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.138 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.38 | w = 1/[σ2(Fo2) + 1.3744P] where P = (Fo2 + 2Fc2)/3 |
1481 reflections | (Δ/σ)max < 0.001 |
108 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.2228 (2) | 0.10315 (15) | 0.11881 (16) | 0.0760 (7) | |
F2 | 0.2173 (4) | −0.0515 (2) | 0.05362 (17) | 0.1020 (9) | |
F3 | 0.2125 (4) | −0.0419 (2) | 0.19661 (18) | 0.1177 (11) | |
O1 | 0.4628 (3) | 0.0027 (2) | 0.1262 (3) | 0.0968 (14) | |
H1 | 0.516 (6) | 0.057 (4) | 0.133 (3) | 0.108 (17)* | |
H2 | 0.515 (6) | −0.053 (4) | 0.128 (3) | 0.109 (17)* | |
O2 | 0.6367 (2) | 0.16850 (14) | 0.13995 (14) | 0.0435 (5) | |
O3 | 0.8588 (2) | 0.33805 (14) | 0.11459 (14) | 0.0425 (5) | |
C1 | 0.8229 (3) | 0.1569 (2) | 0.1462 (2) | 0.0409 (7) | |
H11 | 0.8705 | 0.1372 | 0.0889 | 0.049* | |
H12 | 0.8511 | 0.1021 | 0.1883 | 0.049* | |
C2 | 0.9021 (4) | 0.2567 (2) | 0.1756 (2) | 0.0435 (8) | |
H21 | 0.8585 | 0.2745 | 0.2341 | 0.052* | |
H22 | 1.0288 | 0.2493 | 0.1792 | 0.052* | |
C3 | 0.6730 (3) | 0.3498 (2) | 0.1084 (2) | 0.0410 (7) | |
H31 | 0.6449 | 0.4046 | 0.0663 | 0.049* | |
H32 | 0.6256 | 0.3696 | 0.1657 | 0.049* | |
C4 | 0.5934 (4) | 0.2498 (2) | 0.0791 (2) | 0.0448 (8) | |
H41 | 0.4666 | 0.2573 | 0.0756 | 0.054* | |
H42 | 0.6366 | 0.2319 | 0.0205 | 0.054* | |
B1 | 0.2712 (4) | 0.0021 (3) | 0.1232 (3) | 0.0412 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0439 (11) | 0.0559 (12) | 0.128 (2) | 0.0169 (9) | 0.0004 (13) | 0.0007 (12) |
F2 | 0.0930 (18) | 0.113 (2) | 0.1005 (19) | −0.0035 (16) | −0.0243 (16) | −0.0500 (16) |
F3 | 0.118 (2) | 0.141 (2) | 0.0942 (19) | −0.035 (2) | 0.0120 (17) | 0.0528 (18) |
O1 | 0.0264 (12) | 0.0294 (13) | 0.234 (4) | 0.0014 (11) | −0.008 (2) | −0.0130 (18) |
O2 | 0.0295 (10) | 0.0357 (10) | 0.0652 (14) | −0.0044 (8) | −0.0025 (9) | 0.0052 (10) |
O3 | 0.0292 (10) | 0.0355 (10) | 0.0629 (14) | −0.0033 (8) | 0.0010 (10) | 0.0012 (10) |
C1 | 0.0308 (16) | 0.0374 (15) | 0.0544 (18) | 0.0027 (12) | −0.0045 (13) | 0.0001 (14) |
C2 | 0.0314 (14) | 0.0430 (17) | 0.056 (2) | 0.0027 (13) | −0.0078 (14) | −0.0035 (14) |
C3 | 0.0318 (15) | 0.0367 (15) | 0.0544 (19) | 0.0014 (12) | −0.0022 (13) | 0.0054 (14) |
C4 | 0.0348 (15) | 0.0442 (17) | 0.055 (2) | −0.0003 (13) | −0.0100 (15) | 0.0025 (14) |
B1 | 0.0299 (16) | 0.0422 (18) | 0.052 (2) | −0.0037 (15) | −0.0039 (18) | 0.0006 (15) |
F1—B1 | 1.361 (4) | C1—C2 | 1.495 (4) |
F2—B1 | 1.332 (4) | C1—H11 | 0.9800 |
F3—B1 | 1.333 (4) | C1—H12 | 0.9800 |
O1—B1 | 1.473 (4) | C2—H21 | 0.9800 |
O1—H1 | 0.82 (5) | C2—H22 | 0.9800 |
O1—H2 | 0.82 (5) | C3—C4 | 1.499 (4) |
O2—C4 | 1.440 (3) | C3—H31 | 0.9800 |
O2—C1 | 1.442 (3) | C3—H32 | 0.9800 |
O3—C3 | 1.439 (3) | C4—H41 | 0.9800 |
O3—C2 | 1.442 (3) | C4—H42 | 0.9800 |
B1—O1—H1 | 121 (3) | O3—C3—H31 | 109.8 |
B1—O1—H2 | 119 (3) | C4—C3—H31 | 109.8 |
H1—O1—H2 | 120 (4) | O3—C3—H32 | 109.8 |
C4—O2—C1 | 110.4 (2) | C4—C3—H32 | 109.8 |
C3—O3—C2 | 110.4 (2) | H31—C3—H32 | 108.2 |
O2—C1—C2 | 109.5 (2) | O2—C4—C3 | 110.1 (2) |
O2—C1—H11 | 109.8 | O2—C4—H41 | 109.6 |
C2—C1—H11 | 109.8 | C3—C4—H41 | 109.6 |
O2—C1—H12 | 109.8 | O2—C4—H42 | 109.6 |
C2—C1—H12 | 109.8 | C3—C4—H42 | 109.6 |
H11—C1—H12 | 108.2 | H41—C4—H42 | 108.2 |
O3—C2—C1 | 110.1 (2) | F3—B1—F2 | 109.9 (3) |
O3—C2—H21 | 109.6 | F3—B1—F1 | 111.0 (3) |
C1—C2—H21 | 109.6 | F2—B1—F1 | 112.1 (3) |
O3—C2—H22 | 109.6 | F3—B1—O1 | 108.3 (3) |
C1—C2—H22 | 109.6 | F2—B1—O1 | 109.8 (3) |
H21—C2—H22 | 108.2 | F1—B1—O1 | 105.6 (3) |
O3—C3—C4 | 109.5 (2) | ||
C4—O2—C1—C2 | 58.7 (3) | C2—O3—C3—C4 | −58.7 (3) |
C3—O3—C2—C1 | 59.2 (3) | C1—O2—C4—C3 | −58.9 (3) |
O2—C1—C2—O3 | −58.6 (3) | O3—C3—C4—O2 | 58.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.82 (5) | 1.72 (5) | 2.534 (3) | 175 (5) |
O1—H2···O3i | 0.82 (5) | 1.72 (5) | 2.539 (3) | 170 (5) |
Symmetry code: (i) −x+3/2, y−1/2, z. |
B1—O1 | 1.473 (4) [0.76] {1.528 (4) [0.65]} | 1.532 (6) [0.64] | 1.512 (2) [0.68] |
B1—F1 | 1.361 (4) [0.81] {1.409 (4) [0.71]} | 1.383 (5) [0.76] | 1.377 (2) [0.77] |
B1—F2 | 1.332 (4) [0.87] {1.396 (4) [0.73]} | 1.399 (5) [0.73] | 1.382 (2) [0.76] |
B1—F3 | 1.333 (4) [0.87] {1.410 (4) [0.71]} | 1.382 (5) [0.76] | 1.390 (2) [0.74] |
Σs(B–O,F) | [3.31] {[2.80]} | [2.89] | [2.96] |
Acknowledgements
We thank E. Hammes and P. Roloff for technical support, and C. Siemes for the preparation of the
scheme.References
Bang, W. B. & Carpenter, G. B. (1964). Acta Cryst. 17, 742–745. CrossRef ICSD IUCr Journals Web of Science Google Scholar
Bartmann, K. & Mootz, D. (1990). Acta Cryst. C46, 319–320. CrossRef CAS IUCr Journals Google Scholar
Berzelius, J. J. (1824). Liebigs Ann. Chem. 46, 48–58. CrossRef Google Scholar
Blessing, R. H. (1989). J. Appl. Cryst. 22, 396–397. CrossRef Web of Science IUCr Journals Google Scholar
Bott, S. B., Alvanipour, A. & Atwood, J. L. (1991). J. Incl. Phenom. Macrocycl. Chem. 10, 153–158. CrossRef CAS Google Scholar
Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244–247. CrossRef CAS Web of Science IUCr Journals Google Scholar
Buschmann, J., Müller, E. & Luger, P. (1986). Acta Cryst. C42, 873–876. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Chekhlov, A. N. (2005). Russ. J. Coord. Chem. 31, 9–13. CrossRef CAS Google Scholar
Christe, K. O., Schack, C. J. & Wilson, R. D. (1975). Inorg. Chem. 14, 2224–2230. CrossRef CAS Google Scholar
Davy, J. (1812). Phil. Trans. R. Soc. 102, 352–363. Google Scholar
Diehl, P. (1958). Helv. Phys. Acta, 31, 685–712. CAS Google Scholar
Dubey, A., Saha, H. P., Pink, R. H., Badu, S. R., Mahato, D. N., Scheicher, R. H., Mahanti, K. M., Chow, L. & Das, T. P. (2007). Hyperfine Interact. 176, 45–50. CrossRef CAS Google Scholar
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126. CrossRef CAS Web of Science Google Scholar
Farcasui, D. & Ghenciu, A. (1992). J. Catal. 134, 126–133. Google Scholar
Feinberg, H., Columbus, I., Cohen, S., Rabinovitz, M., Selig, H. & Shoham, G. (1993). Polyhedron, 12, 2913–2919. CSD CrossRef CAS Web of Science Google Scholar
Fonar, M. S., Simonov, Y. A., Mazus, M. D., Ganin, E. V. & Gelmboldt, V. O. (1997). Crystallogr. Rep. 42, 790–794. Google Scholar
Ford, P. T. & Richards, R. E. (1956). J. Chem. Soc. pp. 3870–3874. CrossRef Google Scholar
Fulmer, G. R., Miller, A. J. M., Sherden, N. H., Gottlieb, H. E., Nudelman, A., Stoltz, B. M., Bercaw, J. E. & Goldberg, K. I. (2010). Organometallics, 29, 2176–2179. Web of Science CrossRef CAS Google Scholar
Gascard, C. & Mascherpa, G. (1973). J. Chim. Phys. 70, 1040–1047. CrossRef CAS Google Scholar
Gay-Lussac, J. L. & Thenard, L. J. (1809). Ann. Phys. 32, 1–15. Google Scholar
Gillespie, R. J. & Hartman, J. S. (1967). Can. J. Chem. 45, 859–863. CrossRef CAS Google Scholar
Gottlieb, H. E., Kotlyar, V. & Nudelman, A. (1997). J. Org. Chem. 62, 7512–7515. CrossRef PubMed CAS Web of Science Google Scholar
Greenwood, N. N. & Martin, R. L. (1951). J. Chem. Soc. pp. 1915–1921. CrossRef Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Gutmann, V. (1976). Coord. Chem. Rev. 18, 225–255. CrossRef CAS Google Scholar
Klinkenberg, L. J. & Ketelaar, J. A. A. (1935). Recl Trav. Chim. Pays Bas, 54, 959–961. CrossRef CAS Google Scholar
Liu, L., Wang, X. & Li, C. (2003). Org. Lett. 5, 361–363. CrossRef PubMed CAS Google Scholar
Matsumoto, K., Hagiwara, R., Mazej, Z., Goreshnik, E. & Žemva, B. (2006). J. Phys. Chem. B, 110, 2138–2141. CrossRef PubMed CAS Google Scholar
McGrath, J. S., Stack, G. G. & McCusker, P. A. (1944). J. Am. Chem. Soc. 66, 1263–1264. CrossRef CAS Google Scholar
Meerwein, H. (1933). Ber. Dtsch Chem. Ges. A/B, 66, 411–414. CrossRef Google Scholar
Meerwein, H. & Pannwitz, W. (1934). J. Prakt. Chem. 141, 123–148. CrossRef CAS Google Scholar
Mootz, D. & Steffen, M. (1981a). Z. Anorg. Allg. Chem. 482, 193–200. CrossRef CAS Google Scholar
Mootz, D. & Steffen, M. (1981b). Z. Anorg. Allg. Chem. 483, 171–180. CrossRef CAS Google Scholar
Mootz, D. & Steffen, M. (1981c). Acta Cryst. B37, 1110–1112. CrossRef CAS IUCr Journals Google Scholar
Orain, P.-Y., Capon, J.-F., Gloaguen, F., Pétillon, F. Y., Schollhammer, P., Talarmin, J., Zampella, G., De Gioia, L. & Roisnel, T. (2010). Inorg. Chem. 49, 5003–5008. CrossRef CAS PubMed Google Scholar
Oyama, T., Hamano, T., Nagumo, K. & Nakane, R. (1978). Bull. Chem. Soc. Jpn, 51, 1441–1443. CrossRef CAS Google Scholar
Pawlenko, S. (1959). Z. Anorg. Allg. Chem. 300, 152–158. CrossRef CAS Google Scholar
Pawlenko, S. (1968). Chem. Ing. Tech. 40, 52–55. CrossRef CAS Google Scholar
Prakash, G. K. S., Gurung, L., Marinez, E. R., Mathew, T. & Olah, G. A. (2016). Tetrahedron Lett. 57, 288–291. CrossRef CAS Google Scholar
Schomaker, V. & Trueblood, K. N. (1968). Acta Cryst. B24, 63–76. CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Simonov, Y. A., Gelmboldt, V. O., Ganin, E. V., Dvorkin, A. A., Fonar, M. S., Ostapchuk, L. V. & Lipkovsky, Y. (1995). Russ. J. Coord. Chem. 21, 724–729. CAS Google Scholar
Stoe & Cie (2009). X-AREA. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar
Van Rijn, J., Reedijk, J., Dartmann, M. & Krebs, B. (1987). J. Chem. Soc. Dalton Trans. pp. 2579–2593. CrossRef Google Scholar
Wamser, C. A. (1951). J. Am. Chem. Soc. 73, 409–416. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yeo, G. A. & Ford, T. A. (2006). S. Afr. J. Chem. 59, 129–134. CAS Google Scholar
Yoneda, N., Hasegawa, E., Aomura, K. & Ohtsuka, H. (1969). Bull. Jpn Petrol. Inst. 11, 54–58. CrossRef CAS Google Scholar
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