Tri-tert-butyl­phospho­nium hy­droxy­tris­(penta­fluoro­phen­yl)borate

Klahn, M.; Spannenberg, A.; Rosenthal, U.

doi:10.1107/S1600536812018144

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1549

doi:10.1107/S1600536812018144

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Tri-tert-butylphosphonium hydroxytris(pentafluorophenyl)borate

Marcus Klahn,^a ^* Anke Spannenberg ^a and Uwe Rosenthal ^a

^aLeibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
^*Correspondence e-mail: marcus.klahn@catalysis.de

(Received 20 April 2012; accepted 23 April 2012; online 28 April 2012)

The ionic title compound, C₁₂H₂₈P⁺·C₁₈HBF₁₅O⁻, was obtained by the stoichiometric reaction of ^tBu₃P, B(C₆F₅)₃ and water in toluene. A weak P—H⋯O hydrogen bond is observed in the crystal structure.

Related literature

For general aspects of related compounds, see: Welch et al. (2007 ); Stephan & Erker (2010 ). For related structures, see: Roesler et al. (2003 ); Di Saverio et al. (2005 ); Welch & Stephan (2007 ).

Experimental

Crystal data

C₁₂H₂₈P⁺·C₁₈HBF₁₅O⁻
M_r = 732.31
Triclinic, $[P \overline 1]$
a = 9.798 (2) Å
b = 12.042 (2) Å
c = 15.389 (3) Å
α = 112.31 (3)°
β = 94.51 (3)°
γ = 108.93 (3)°
V = 1546.2 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 200 K
0.30 × 0.23 × 0.15 mm

Data collection

Stoe IPDS II diffractometer
24084 measured reflections
6557 independent reflections
4256 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.069
S = 0.84
6557 reflections
450 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
P1—H2⋯O1ⁱ	1.288 (14)	2.276 (14)	3.4080 (13)	144.6 (9)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2005 ); cell refinement: X-AREA; data reduction: X-RED32; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812018144/hg5215sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812018144/hg5215Isup2.hkl

checkCIF report

Comment top

The concept of "frustrated Lewis pairs" has been explored in depth and coined by Welch et al. (2007). The key issue is the sterical hindrance between the Lewis acids and bases preventing a classical adduct formation which gives rise to a unique reactivity due to the interaction of the basic and acidic centres. During the last years, this feature has been shown in reactions with a wide variety of reagents, these can be either small molecules like H₂, CO₂, and N₂O, or larger ones like terminal olefins, alkynes, dienes, B–H bonds, disulfides and the C–O bonds of cyclic ethers (Stephan & Erker 2010). The reaction of tri-tert-butylphosphine, tris(pentafluorophenyl)borane and water proceeds in a similar way to the conversion of tris(pentafluorophenyl)borane with water in the presence of triethylamine (Di Saverio et al., 2005). Roesler et al. (2003) obtained an intramolecular salt of the type 1-[N(H)Ph₂]-2-[B(OH)(C₆F₅)₂]C₆H₄ with a phenyl bridge between nitrogen and boron. The title compound consists of the phosphonium cation [tBu₃PH]⁺ and the boranate anion [HOB(C₆F₅)₃]^- (Figure 1), which are probably generated via subsequent protonation of the phosphine by the formed borane water adduct. The phosphonium cation is comparable to that in the compound [tBu₃PH][HB(C₆F₅)₃], which is the product of dihydrogen activation (Welch & Stephan 2007). Besides the unexceptional metric parameters both ions exhibit a geometry of a distorted tetrahedron at the phosphorous and the boron centre, respectively. Noteworthy, a weak P—H···O hydrogen bond was obtained with following geometric parameters: P1—H2 1.288 (14), H2···O1 2.276 (14), P1···O1 3.4080 (13) Å, P1—H2···O1 144.6 (9)°.

Related literature top

For general aspects of related compounds, see: Welch et al. (2007); Stephan & Erker (2010). For related structures, see: Roesler et al. (2003); Di Saverio et al. (2005); Welch & Stephan (2007).

Experimental top

Solid tris(pentafluorophenyl)borane (0.256 g, 0.5 mmol) and tri-tert-butylphosphine (0.101 g, 0.5 mmol) were dissolved in 20 ml of toluene resulting in a pale yellow solution. After stirring this mixture for 30 minutes 9 µL of water (0.5 mmol) was added. The reaction mixture was allowed to stir for 12 h at 40 °C during which the solution turned colorless. The reaction was concentrated until the first precipitate was formed, which was resolved by gentle heating. Leaving the solution at -78 °C gave colorless prisms in an isolated yield of 0.127 g (35%) The colorless compound was fully characterized by standard analytical methods, NMR (295 K, CDCl₃): ¹H: d = 5.96 (d, 1H, ¹J_HP = 451 Hz, PH), 2.05 (br s, 1H, HOB), 1.58 (d, 27H, ³J_HP = 15.3 Hz, {(CH₃)₃C}₃). ¹¹B: d = -3.74 (s). ³¹P{¹H}: d = 54.8 (s). ³¹P: d = 54.8 (dm, ¹J_PH = 452 Hz, ³J_HP = 15.4 Hz). ¹⁹F: d = -135.0 (d, 6 F, ³J_FF = 21.6 Hz, o-F), -161.8 (t, 3 F, ³J_FF = 20.1 Hz, p-F), -165.5 (m, 6 F, m-F).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-RED32 (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with atom labels and 30% displacement ellipsoids. Hydrogen atoms at carbon atoms are omitted for clarity.

Tri-tert-butylphosphonium hydroxytris(pentafluorophenyl)borate top

Crystal data top

C₁₂H₂₈P⁺·C₁₈HBF₁₅O⁻	Z = 2
M_r = 732.31	F(000) = 744
Triclinic, P1	D_x = 1.573 Mg m⁻³
a = 9.798 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.042 (2) Å	Cell parameters from 5729 reflections
c = 15.389 (3) Å	θ = 1.5–27.2°
α = 112.31 (3)°	µ = 0.21 mm⁻¹
β = 94.51 (3)°	T = 200 K
γ = 108.93 (3)°	Prism, colourless
V = 1546.2 (8) Å³	0.30 × 0.23 × 0.15 mm

Data collection top

Stoe IPDS II diffractometer	4256 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 26.7°, θ_min = 1.5°
ω scans	h = −12→12
24084 measured reflections	k = −15→15
6557 independent reflections	l = −19→19

Refinement top

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 0.84	w = 1/[σ²(F_o²) + (0.0383P)²] where P = (F_o² + 2F_c²)/3
6557 reflections	(Δ/σ)_max = 0.001
450 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₂H₂₈P⁺·C₁₈HBF₁₅O⁻	γ = 108.93 (3)°
M_r = 732.31	V = 1546.2 (8) Å³
Triclinic, P1	Z = 2
a = 9.798 (2) Å	Mo Kα radiation
b = 12.042 (2) Å	µ = 0.21 mm⁻¹
c = 15.389 (3) Å	T = 200 K
α = 112.31 (3)°	0.30 × 0.23 × 0.15 mm
β = 94.51 (3)°

Data collection top

Stoe IPDS II diffractometer	4256 reflections with I > 2σ(I)
24084 measured reflections	R_int = 0.031
6557 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 0.84	Δρ_max = 0.20 e Å⁻³
6557 reflections	Δρ_min = −0.24 e Å⁻³
450 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.23991 (17)	0.30327 (14)	0.67250 (11)	0.0311 (3)
C2	0.33984 (17)	0.36491 (15)	0.63024 (11)	0.0341 (3)
C3	0.37910 (19)	0.30153 (17)	0.54731 (12)	0.0391 (4)
C4	0.3198 (2)	0.16833 (17)	0.50170 (11)	0.0421 (4)
C5	0.22222 (19)	0.10115 (15)	0.54084 (12)	0.0404 (4)
C6	0.18568 (18)	0.16856 (15)	0.62327 (11)	0.0348 (4)
C7	−0.00162 (17)	0.30725 (14)	0.73956 (10)	0.0311 (3)
C8	−0.08453 (17)	0.32198 (14)	0.67075 (11)	0.0327 (3)
C9	−0.23652 (18)	0.26740 (15)	0.64192 (11)	0.0366 (4)
C10	−0.31631 (18)	0.19121 (16)	0.68202 (12)	0.0390 (4)
C11	−0.24162 (19)	0.17148 (16)	0.74982 (12)	0.0397 (4)
C12	−0.08921 (18)	0.22759 (15)	0.77625 (11)	0.0362 (4)
C13	0.25420 (17)	0.37488 (14)	0.86700 (11)	0.0320 (3)
C14	0.22187 (18)	0.44094 (15)	0.95346 (11)	0.0365 (4)
C15	0.2796 (2)	0.45011 (17)	1.04117 (12)	0.0443 (4)
C16	0.37549 (19)	0.39040 (18)	1.04639 (12)	0.0453 (4)
C17	0.41270 (18)	0.32459 (16)	0.96440 (13)	0.0420 (4)
C18	0.35269 (18)	0.31783 (15)	0.87707 (11)	0.0361 (4)
C19	0.8368 (2)	0.14093 (16)	0.09712 (12)	0.0437 (4)
C20	0.9725 (2)	0.1684 (2)	0.05404 (14)	0.0576 (5)
H20A	1.0453	0.1429	0.0805	0.086*
H20B	1.0168	0.2614	0.0703	0.086*
H20C	0.9424	0.1185	−0.0163	0.086*
C21	0.7709 (3)	−0.00456 (17)	0.07480 (16)	0.0636 (6)
H21A	0.7464	−0.0570	0.0048	0.095*
H21B	0.6809	−0.0233	0.0994	0.095*
H21C	0.8436	−0.0258	0.1060	0.095*
C22	0.7245 (2)	0.1750 (2)	0.04734 (13)	0.0587 (5)
H22A	0.7639	0.2688	0.0660	0.088*
H22B	0.6308	0.1499	0.0672	0.088*
H22C	0.7072	0.1280	−0.0228	0.088*
C23	0.7343 (2)	0.20913 (17)	0.29229 (14)	0.0449 (4)
C24	0.7288 (3)	0.0981 (2)	0.32003 (18)	0.0687 (6)
H24A	0.6500	0.0829	0.3546	0.103*
H24B	0.8243	0.1218	0.3617	0.103*
H24C	0.7087	0.0187	0.2615	0.103*
C25	0.5834 (2)	0.1725 (2)	0.22956 (17)	0.0599 (5)
H25A	0.5591	0.0906	0.1724	0.090*
H25B	0.5872	0.2413	0.2094	0.090*
H25C	0.5072	0.1622	0.2667	0.090*
C26	0.7618 (2)	0.33412 (19)	0.38274 (14)	0.0550 (5)
H26A	0.6741	0.3231	0.4102	0.082*
H26B	0.7811	0.4070	0.3651	0.082*
H26C	0.8476	0.3519	0.4305	0.082*
C27	1.0711 (2)	0.27172 (17)	0.29329 (13)	0.0446 (4)
C28	1.0933 (3)	0.3432 (2)	0.40278 (14)	0.0666 (6)
H28A	1.1960	0.3669	0.4344	0.100*
H28B	1.0257	0.2863	0.4258	0.100*
H28C	1.0726	0.4220	0.4182	0.100*
C29	1.1911 (2)	0.3614 (2)	0.26475 (16)	0.0611 (5)
H29A	1.1724	0.4403	0.2759	0.092*
H29B	1.1889	0.3162	0.1963	0.092*
H29C	1.2887	0.3850	0.3038	0.092*
C30	1.0909 (2)	0.1425 (2)	0.26836 (17)	0.0614 (5)
H30A	1.0789	0.0978	0.1985	0.092*
H30B	1.0161	0.0876	0.2892	0.092*
H30C	1.1901	0.1597	0.3015	0.092*
F1	0.40912 (11)	0.49630 (8)	0.67088 (7)	0.0447 (2)
F2	0.47413 (12)	0.36859 (11)	0.50949 (8)	0.0551 (3)
F3	0.35817 (14)	0.10532 (11)	0.42120 (7)	0.0622 (3)
F4	0.16501 (13)	−0.02981 (9)	0.49855 (7)	0.0580 (3)
F5	0.09291 (11)	0.09601 (8)	0.65966 (7)	0.0454 (2)
F6	−0.01457 (10)	0.39236 (9)	0.62464 (7)	0.0459 (2)
F7	−0.30771 (11)	0.28541 (11)	0.57324 (8)	0.0575 (3)
F8	−0.46452 (11)	0.13439 (11)	0.65281 (8)	0.0570 (3)
F9	−0.31768 (12)	0.09451 (11)	0.78874 (8)	0.0612 (3)
F10	−0.02586 (11)	0.19765 (10)	0.84141 (7)	0.0538 (3)
F11	0.12531 (11)	0.49906 (10)	0.95367 (7)	0.0494 (3)
F12	0.24301 (13)	0.51617 (12)	1.12182 (7)	0.0662 (3)
F13	0.43409 (12)	0.39742 (12)	1.13126 (8)	0.0681 (3)
F14	0.51001 (12)	0.26803 (10)	0.96855 (8)	0.0599 (3)
F15	0.39801 (12)	0.25147 (10)	0.80060 (7)	0.0517 (3)
B1	0.1813 (2)	0.37833 (16)	0.76764 (12)	0.0312 (4)
O1	0.21571 (15)	0.51498 (10)	0.78731 (8)	0.0353 (3)
P1	0.88590 (5)	0.24737 (4)	0.22942 (3)	0.03315 (10)
H1	0.304 (3)	0.549 (2)	0.7996 (15)	0.067 (8)*
H2	0.9035 (16)	0.3605 (13)	0.2343 (10)	0.027 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0295 (8)	0.0347 (8)	0.0334 (8)	0.0150 (7)	0.0059 (7)	0.0172 (7)
C2	0.0318 (9)	0.0358 (8)	0.0390 (8)	0.0150 (7)	0.0073 (7)	0.0189 (7)
C3	0.0397 (10)	0.0534 (10)	0.0409 (9)	0.0263 (8)	0.0163 (8)	0.0289 (8)
C4	0.0503 (11)	0.0557 (11)	0.0319 (8)	0.0342 (9)	0.0142 (8)	0.0182 (8)
C5	0.0458 (10)	0.0352 (9)	0.0377 (9)	0.0213 (8)	0.0025 (8)	0.0097 (7)
C6	0.0345 (9)	0.0348 (8)	0.0398 (9)	0.0145 (7)	0.0082 (7)	0.0198 (7)
C7	0.0332 (9)	0.0307 (8)	0.0319 (8)	0.0134 (7)	0.0091 (7)	0.0148 (7)
C8	0.0334 (9)	0.0343 (8)	0.0352 (8)	0.0134 (7)	0.0114 (7)	0.0187 (7)
C9	0.0335 (9)	0.0427 (9)	0.0374 (9)	0.0178 (8)	0.0062 (7)	0.0187 (7)
C10	0.0257 (9)	0.0424 (9)	0.0425 (9)	0.0095 (7)	0.0073 (7)	0.0146 (8)
C11	0.0378 (10)	0.0387 (9)	0.0397 (9)	0.0057 (8)	0.0136 (8)	0.0203 (7)
C12	0.0370 (9)	0.0382 (8)	0.0350 (8)	0.0116 (7)	0.0050 (7)	0.0204 (7)
C13	0.0283 (8)	0.0294 (8)	0.0370 (8)	0.0079 (7)	0.0060 (7)	0.0159 (7)
C14	0.0313 (9)	0.0385 (9)	0.0396 (9)	0.0100 (7)	0.0082 (7)	0.0194 (7)
C15	0.0406 (10)	0.0492 (10)	0.0348 (9)	0.0055 (8)	0.0103 (8)	0.0192 (8)
C16	0.0354 (10)	0.0546 (10)	0.0408 (10)	0.0007 (8)	−0.0006 (8)	0.0310 (9)
C17	0.0294 (9)	0.0408 (9)	0.0577 (11)	0.0063 (8)	−0.0014 (8)	0.0312 (9)
C18	0.0350 (9)	0.0321 (8)	0.0403 (9)	0.0117 (7)	0.0049 (7)	0.0164 (7)
C19	0.0522 (11)	0.0369 (9)	0.0435 (9)	0.0211 (8)	0.0118 (8)	0.0153 (8)
C20	0.0748 (15)	0.0619 (12)	0.0485 (11)	0.0353 (11)	0.0290 (10)	0.0258 (10)
C21	0.0714 (15)	0.0362 (10)	0.0717 (14)	0.0204 (10)	0.0136 (11)	0.0124 (10)
C22	0.0717 (14)	0.0570 (12)	0.0429 (10)	0.0320 (11)	0.0009 (10)	0.0133 (9)
C23	0.0444 (10)	0.0458 (10)	0.0623 (11)	0.0212 (8)	0.0261 (9)	0.0354 (9)
C24	0.0778 (16)	0.0680 (13)	0.1029 (17)	0.0370 (12)	0.0521 (14)	0.0663 (13)
C25	0.0424 (12)	0.0564 (12)	0.0889 (15)	0.0177 (10)	0.0245 (11)	0.0386 (11)
C26	0.0655 (13)	0.0676 (12)	0.0562 (11)	0.0395 (11)	0.0346 (10)	0.0355 (10)
C27	0.0419 (10)	0.0530 (10)	0.0504 (10)	0.0231 (9)	0.0111 (8)	0.0296 (9)
C28	0.0649 (14)	0.0878 (16)	0.0520 (12)	0.0383 (13)	0.0014 (10)	0.0298 (11)
C29	0.0392 (11)	0.0630 (13)	0.0807 (14)	0.0134 (10)	0.0118 (10)	0.0362 (12)
C30	0.0594 (13)	0.0714 (13)	0.0835 (15)	0.0420 (11)	0.0229 (11)	0.0483 (12)
F1	0.0430 (6)	0.0367 (5)	0.0561 (6)	0.0122 (4)	0.0195 (5)	0.0226 (5)
F2	0.0597 (7)	0.0738 (7)	0.0633 (6)	0.0378 (6)	0.0376 (6)	0.0465 (6)
F3	0.0838 (8)	0.0728 (7)	0.0429 (6)	0.0491 (7)	0.0274 (6)	0.0195 (5)
F4	0.0728 (8)	0.0373 (5)	0.0535 (6)	0.0250 (5)	0.0081 (5)	0.0069 (5)
F5	0.0507 (6)	0.0336 (5)	0.0567 (6)	0.0164 (5)	0.0192 (5)	0.0227 (5)
F6	0.0402 (6)	0.0579 (6)	0.0502 (6)	0.0138 (5)	0.0100 (4)	0.0383 (5)
F7	0.0407 (6)	0.0777 (7)	0.0643 (7)	0.0211 (6)	0.0008 (5)	0.0443 (6)
F8	0.0284 (6)	0.0688 (7)	0.0674 (7)	0.0095 (5)	0.0086 (5)	0.0309 (6)
F9	0.0486 (7)	0.0672 (7)	0.0612 (7)	−0.0018 (5)	0.0127 (5)	0.0409 (6)
F10	0.0472 (6)	0.0596 (6)	0.0576 (6)	0.0051 (5)	−0.0003 (5)	0.0433 (5)
F11	0.0513 (6)	0.0613 (6)	0.0453 (5)	0.0316 (5)	0.0204 (5)	0.0227 (5)
F12	0.0705 (8)	0.0830 (8)	0.0378 (6)	0.0220 (7)	0.0194 (5)	0.0233 (6)
F13	0.0519 (7)	0.1004 (9)	0.0526 (6)	0.0096 (6)	−0.0018 (5)	0.0525 (7)
F14	0.0465 (6)	0.0617 (7)	0.0822 (8)	0.0207 (5)	−0.0019 (6)	0.0451 (6)
F15	0.0572 (7)	0.0556 (6)	0.0500 (6)	0.0372 (5)	0.0086 (5)	0.0184 (5)
B1	0.0332 (10)	0.0296 (9)	0.0341 (9)	0.0124 (8)	0.0079 (8)	0.0168 (7)
O1	0.0356 (7)	0.0298 (6)	0.0430 (6)	0.0130 (5)	0.0090 (5)	0.0179 (5)
P1	0.0358 (2)	0.0319 (2)	0.0392 (2)	0.01505 (18)	0.01272 (18)	0.02023 (18)

Geometric parameters (Å, º) top

C1—C2	1.388 (2)	C19—P1	1.8667 (19)
C1—C6	1.390 (2)	C20—H20A	0.9800
C1—B1	1.660 (2)	C20—H20B	0.9800
C2—F1	1.3567 (18)	C20—H20C	0.9800
C2—C3	1.374 (2)	C21—H21A	0.9800
C3—F2	1.3461 (19)	C21—H21B	0.9800
C3—C4	1.371 (2)	C21—H21C	0.9800
C4—F3	1.3405 (19)	C22—H22A	0.9800
C4—C5	1.375 (2)	C22—H22B	0.9800
C5—F4	1.3471 (19)	C22—H22C	0.9800
C5—C6	1.369 (2)	C23—C25	1.531 (3)
C6—F5	1.3562 (18)	C23—C26	1.537 (3)
C7—C8	1.383 (2)	C23—C24	1.538 (2)
C7—C12	1.389 (2)	C23—P1	1.8639 (18)
C7—B1	1.653 (2)	C24—H24A	0.9800
C8—F6	1.3593 (17)	C24—H24B	0.9800
C8—C9	1.373 (2)	C24—H24C	0.9800
C9—F7	1.3442 (18)	C25—H25A	0.9800
C9—C10	1.369 (2)	C25—H25B	0.9800
C10—F8	1.3410 (19)	C25—H25C	0.9800
C10—C11	1.364 (2)	C26—H26A	0.9800
C11—F9	1.3478 (18)	C26—H26B	0.9800
C11—C12	1.376 (2)	C26—H26C	0.9800
C12—F10	1.3574 (17)	C27—C28	1.532 (3)
C13—C18	1.384 (2)	C27—C30	1.536 (2)
C13—C14	1.389 (2)	C27—C29	1.536 (3)
C13—B1	1.657 (2)	C27—P1	1.8710 (19)
C14—F11	1.3466 (19)	C28—H28A	0.9800
C14—C15	1.371 (2)	C28—H28B	0.9800
C15—F12	1.345 (2)	C28—H28C	0.9800
C15—C16	1.369 (3)	C29—H29A	0.9800
C16—F13	1.3451 (18)	C29—H29B	0.9800
C16—C17	1.362 (3)	C29—H29C	0.9800
C17—F14	1.3497 (19)	C30—H30A	0.9800
C17—C18	1.386 (2)	C30—H30B	0.9800
C18—F15	1.3489 (19)	C30—H30C	0.9800
C19—C20	1.528 (3)	B1—O1	1.469 (2)
C19—C22	1.538 (2)	O1—H1	0.79 (2)
C19—C21	1.542 (2)	P1—H2	1.288 (14)

C2—C1—C6	112.68 (14)	H21A—C21—H21C	109.5
C2—C1—B1	125.07 (13)	H21B—C21—H21C	109.5
C6—C1—B1	122.16 (14)	C19—C22—H22A	109.5
F1—C2—C3	114.64 (14)	C19—C22—H22B	109.5
F1—C2—C1	120.90 (14)	H22A—C22—H22B	109.5
C3—C2—C1	124.45 (15)	C19—C22—H22C	109.5
F2—C3—C4	119.39 (15)	H22A—C22—H22C	109.5
F2—C3—C2	120.84 (15)	H22B—C22—H22C	109.5
C4—C3—C2	119.77 (15)	C25—C23—C26	106.75 (16)
F3—C4—C3	120.34 (16)	C25—C23—C24	108.96 (16)
F3—C4—C5	120.90 (16)	C26—C23—C24	110.57 (16)
C3—C4—C5	118.75 (15)	C25—C23—P1	111.06 (13)
F4—C5—C6	120.76 (16)	C26—C23—P1	107.30 (13)
F4—C5—C4	119.86 (15)	C24—C23—P1	112.07 (13)
C6—C5—C4	119.38 (15)	C23—C24—H24A	109.5
F5—C6—C5	116.17 (14)	C23—C24—H24B	109.5
F5—C6—C1	118.86 (14)	H24A—C24—H24B	109.5
C5—C6—C1	124.94 (15)	C23—C24—H24C	109.5
C8—C7—C12	112.44 (14)	H24A—C24—H24C	109.5
C8—C7—B1	120.11 (13)	H24B—C24—H24C	109.5
C12—C7—B1	127.43 (13)	C23—C25—H25A	109.5
F6—C8—C9	115.40 (13)	C23—C25—H25B	109.5
F6—C8—C7	119.61 (14)	H25A—C25—H25B	109.5
C9—C8—C7	124.97 (14)	C23—C25—H25C	109.5
F7—C9—C10	119.58 (15)	H25A—C25—H25C	109.5
F7—C9—C8	120.82 (14)	H25B—C25—H25C	109.5
C10—C9—C8	119.58 (14)	C23—C26—H26A	109.5
F8—C10—C11	121.04 (15)	C23—C26—H26B	109.5
F8—C10—C9	120.31 (15)	H26A—C26—H26B	109.5
C11—C10—C9	118.63 (15)	C23—C26—H26C	109.5
F9—C11—C10	119.66 (15)	H26A—C26—H26C	109.5
F9—C11—C12	120.45 (15)	H26B—C26—H26C	109.5
C10—C11—C12	119.86 (14)	C28—C27—C30	109.52 (16)
F10—C12—C11	115.05 (14)	C28—C27—C29	106.15 (17)
F10—C12—C7	120.43 (14)	C30—C27—C29	110.30 (16)
C11—C12—C7	124.51 (14)	C28—C27—P1	110.65 (14)
C18—C13—C14	113.37 (14)	C30—C27—P1	112.04 (14)
C18—C13—B1	127.75 (14)	C29—C27—P1	108.01 (12)
C14—C13—B1	118.80 (13)	C27—C28—H28A	109.5
F11—C14—C15	115.91 (15)	C27—C28—H28B	109.5
F11—C14—C13	119.51 (14)	H28A—C28—H28B	109.5
C15—C14—C13	124.57 (16)	C27—C28—H28C	109.5
F12—C15—C16	119.63 (15)	H28A—C28—H28C	109.5
F12—C15—C14	121.01 (17)	H28B—C28—H28C	109.5
C16—C15—C14	119.36 (17)	C27—C29—H29A	109.5
F13—C16—C17	119.98 (17)	C27—C29—H29B	109.5
F13—C16—C15	120.87 (18)	H29A—C29—H29B	109.5
C17—C16—C15	119.15 (15)	C27—C29—H29C	109.5
F14—C17—C16	119.98 (15)	H29A—C29—H29C	109.5
F14—C17—C18	120.08 (17)	H29B—C29—H29C	109.5
C16—C17—C18	119.93 (15)	C27—C30—H30A	109.5
F15—C18—C13	121.25 (14)	C27—C30—H30B	109.5
F15—C18—C17	115.12 (14)	H30A—C30—H30B	109.5
C13—C18—C17	123.63 (16)	C27—C30—H30C	109.5
C20—C19—C22	106.21 (15)	H30A—C30—H30C	109.5
C20—C19—C21	109.34 (16)	H30B—C30—H30C	109.5
C22—C19—C21	109.95 (16)	O1—B1—C7	106.05 (13)
C20—C19—P1	110.77 (13)	O1—B1—C13	107.91 (13)
C22—C19—P1	108.44 (12)	C7—B1—C13	111.45 (13)
C21—C19—P1	111.96 (13)	O1—B1—C1	111.68 (13)
C19—C20—H20A	109.5	C7—B1—C1	106.95 (13)
C19—C20—H20B	109.5	C13—B1—C1	112.63 (12)
H20A—C20—H20B	109.5	B1—O1—H1	106.0 (16)
C19—C20—H20C	109.5	C23—P1—C19	114.47 (9)
H20A—C20—H20C	109.5	C23—P1—C27	114.13 (8)
H20B—C20—H20C	109.5	C19—P1—C27	113.94 (9)
C19—C21—H21A	109.5	C23—P1—H2	105.0 (6)
C19—C21—H21B	109.5	C19—P1—H2	103.9 (6)
H21A—C21—H21B	109.5	C27—P1—H2	103.7 (6)
C19—C21—H21C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
P1—H2···O1ⁱ	1.288 (14)	2.276 (14)	3.4080 (13)	144.6 (9)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₂₈P⁺·C₁₈HBF₁₅O⁻
M_r	732.31
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	9.798 (2), 12.042 (2), 15.389 (3)
α, β, γ (°)	112.31 (3), 94.51 (3), 108.93 (3)
V (Å³)	1546.2 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.30 × 0.23 × 0.15

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	24084, 6557, 4256
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.069, 0.84
No. of reflections	6557
No. of parameters	450
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.24

Computer programs: X-AREA (Stoe & Cie, 2005), X-RED32 (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
P1—H2···O1ⁱ	1.288 (14)	2.276 (14)	3.4080 (13)	144.6 (9)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

This work was supported by the Leibniz-Institut für Katalyse e·V. an der Universität Rostock.

References

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