(Biphenyl-2,2′-di­yl)di-tert-butyl­phos­phonium trifluoro­methane­sulfonate

Muller, A.; Holzapfel, C.W.

doi:10.1107/S1600536812049045

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 1| January 2013| Page o20

https://doi.org/10.1107/S1600536812049045

Open

access

(Biphenyl-2,2′-diyl)di-tert-butylphosphonium trifluoromethanesulfonate

Alfred Muller ^a ^* and Cedric W. Holzapfel ^a

^aDepartment of Chemistry, University of Johannesburg (APK Campus), PO Box 524, Auckland Park, Johannesburg, 2006, South Africa
^*Correspondence e-mail: mullera@uj.ac.za

(Received 15 November 2012; accepted 29 November 2012; online 5 December 2012)

To aid in the elucidation of catalytic reaction mechanism of palladacycles, we found that reaction of trifluoromethanesulfonic acid with a phosphapalladacycle resulted in elimination of the palladium and formation of the title phospholium salt, C₂₀H₂₆P⁺·CF₃SO₃⁻. Selected geometrical parameters include P—biphenyl (av.) = 1.801 (3) Å and P—t-Bu (av.) = 1.858 (3) Å, and significant distortion of the tetrahedral P-atom environment with biphenyl—P—biphenyl = 93.93 (13)° and t-Bu—P—t-Bu = 118.82 (14)°. In the crystal, weak C—H⋯O interactions lead to channels along the c axis that are occupied by CF₃SO₃⁻ anions.

Related literature

For background to catalytic studies on palladacycles, see: Herrman et al. (2003 ); Beletskaya & Cheprakov (2004 ); Omondi et al. (2011 ); Williams et al. (2008 ); d'Orlye & Jutland (2005 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₂₀H₂₆P⁺·CF₃O₃S⁻
M_r = 446.45
Tetragonal, P 4₁ 2₁ 2
a = 12.1339 (10) Å
c = 30.057 (2) Å
V = 4425.4 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.4 × 0.26 × 0.2 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.902, T_max = 0.949
25275 measured reflections
5502 independent reflections
3241 reflections with I > 2σ(I)
R_int = 0.101

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.117
S = 0.99
5502 reflections
268 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ), 2283 Friedel pairs
Flack parameter: 0.05 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.49	3.381 (4)	161
C19—H19A⋯O2ⁱⁱ	0.96	2.52	3.458 (4)	165
C11—H11⋯O3ⁱⁱⁱ	0.93	2.70	3.601 (4)	162
C15—H15B⋯O3ⁱⁱⁱ	0.96	2.69	3.470 (4)	138
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+{\script{7\over 4}}]$ ; (ii) y, x, -z+2; (iii) x+1, y, z.

Data collection: SMART-NT (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 2012 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812049045/aa2079sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049045/aa2079Isup2.hkl

checkCIF report

Comment top

The introduction of a cyclopalladated compound as a robust catalyst (Herrman et al., 2003) for Heck and cross-coupling reactions resulted in the design of structurally related palladacycles, phosphapalladacycles in particular (Beletskaya & Cheprakov, 2004). However, growing evidence suggests that palladacycles are disassembled during the pre-activation stage to yield low ligated Pd⁰ species as the actual catalyst (d'Orlye & Jutland, 2005). This is further exemplified by our finding that the use of palladacycle (II in Fig. 1), an effective amination catalyst (Beletskaya & Cheprakov, 2004), as a source of palladium together with triphenylphosphine and a strong acid provided an extremely active catalytic system for the hydromethoxylation of alkenes (Omondi et al., 2011 and Williams et al., 2008). In the reaction medium compound II (Fig. 1) was rapidly converted into tetrakistriphenylphosphinepalladium(0) which acted as the actual catalyst. The facile formation of Pd⁰ resulted from acid catalyzed elimination from the palladacycle. This treatment of II with ten equivalents of trifluoromethanesulfonic acid at room temperature resulted in the formation of colloidal palladium and the title compound (I in Fig. 1), the structure of which was confirmed by single-crystal X-ray crystallography.

The title compound I (Fig. 2 and Scheme 1) is a salt consisting of phospholium cations and trifluoromethanesulfonate anions. All ions lie on general positions in the unit cell with no discernible differences in the bond distances of the coordination polyhedron of the phosphorus environment. The bond angles at the phosphorus center shows significant deviations from the expected 109.5° for the tetrahedral shape with biphenyl—P—biphenyl = 93.93 (13)° and t-Bu—P—t-Bu = 118.82 (14)°. These deviations can be ascribed to the somewhat strained 5-membered cyclisation of the dibenzo fragment to form the phospholium ring. This pinching effect in turn allows for more space for the bulky tertiary butyl groups positioned above and below the plane formed by the tricyclic phospholium conjugate and hence the observed t-Bu—P—t-Bu angle. The tricyclic phospholium conjugate marginally deviates from planarity (C1—C6—C7—C12 = 1.9 (4)°), and would have been the primary route to alleviate stress from the pinching effect. Data extracted from the Cambridge Structural Database (Allen, 2002) for the torsion angle between the planes shows a mean value of 1.72° (126 observations). The general trend seems to be that substituents opposite the phospholium cycle forces it to be planar. The preferred orientation of the tertiary butyls are due to several weak C—H···O interactions observed between ions (see Table 1).

Related literature top

For background to catalytic studies on palladacycles, see: Herrman et al. (2003); Beletskaya & Cheprakov (2004); Omondi et al. (2011); Williams et al. (2008); d'Orlye & Jutland (2005). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Trifluorometanesulfonic acid (150 mg, 1 mmol) in 5 ml me thanol was added dropwise to a stirred solution of (acetato-κ²O,O')[2'-(di-tert- butylphosphanyl)-1,1'-biphenyl-κ²P,C²]palladium (462 mg, 1 mmol) in dichloromethane (30 ml) at room temperature under argon. The solution changed from colourless to deep purple and then to dark brown over a period of 10 min. After several hours at room temperature a fine precipitate of palladium black started to form. After 24 h the reaction mixture was filtered through celite to remove the palladium. The solvent was removed in vacuo and the residue distributed between water (15 ml) and ether (15 ml). The aqueous phase was extracted with dichloromethane (3 x 30 ml). The combined extract furnished crystalline (413 mg, 82%) on removal of the solvent in vacuo. Good crystals (mp. 157 – 159 °C) was obtained by diffusion of the vapours of ether into a solution in dichloromethane. Analytical data: ¹H-NMR: δ 1.45 (18H, d, J = 17 Hz), 7.68 (2H, dt, J = 2.5 and 7.5 Hz), 7.85 (2H, t, J = 7.8 Hz), 7.99 (2H, t, J = 7.8 Hz), and 8.64 (2H, dd, J = 2.5 and 7.8 Hz) ¹³C{H}-NMR: δ 26.74 (s), 36.42 (d, J = 42 Hz), 118.72 (d, J = 101 Hz), 123.58 (d, J = 12.3 Hz), 130.90 (d, J = 14.0 Hz), 131.90 (d, J = 14.0 Hz), 131.67 (d, J = 11.4 Hz), 135.95 (d, J = 2.7 Hz), 144.97 (d, J = 17.4 Hz) ³¹P-NMR: δ 51.24

Structure description top

For background to catalytic studies on palladacycles, see: Herrman et al. (2003); Beletskaya & Cheprakov (2004); Omondi et al. (2011); Williams et al. (2008); d'Orlye & Jutland (2005). For a description of the Cambridge Structural Database, see: Allen (2002).

Computing details top

Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 2008); data reduction: SAINT-Plus and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. Proposed reaction scheme of the elimination of the palladium and formation of the title phospholium compound.
	Fig. 2. View of title compound showing displacement ellipsoids (drawn at a 30% probability level) and numbering scheme. Hydrogen atoms have been omitted for clarity.

(Biphenyl-2,2'-diyl)di-tert-butylphosphonium trifluoromethanesulfonate top

Crystal data top

C₂₀H₂₆P⁺·CF₃O₃S⁻	D_x = 1.34 Mg m⁻³
M_r = 446.45	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₁2₁2	Cell parameters from 3572 reflections
Hall symbol: P 4abw 2nw	θ = 2.5–21.9°
a = 12.1339 (10) Å	µ = 0.26 mm⁻¹
c = 30.057 (2) Å	T = 293 K
V = 4425.4 (6) Å³	Prism, yellow
Z = 8	0.4 × 0.26 × 0.2 mm
F(000) = 1872

Data collection top

Bruker SMART 1K CCD diffractometer	3241 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.101
π scans	θ_max = 28.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→16
T_min = 0.902, T_max = 0.949	k = −11→16
25275 measured reflections	l = −39→28
5502 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0519P)²] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
5502 reflections	Δρ_max = 0.17 e Å⁻³
268 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 2283 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (11)

Crystal data top

C₂₀H₂₆P⁺·CF₃O₃S⁻	Z = 8
M_r = 446.45	Mo Kα radiation
Tetragonal, P4₁2₁2	µ = 0.26 mm⁻¹
a = 12.1339 (10) Å	T = 293 K
c = 30.057 (2) Å	0.4 × 0.26 × 0.2 mm
V = 4425.4 (6) Å³

Data collection top

Bruker SMART 1K CCD diffractometer	5502 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	3241 reflections with I > 2σ(I)
T_min = 0.902, T_max = 0.949	R_int = 0.101
25275 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	H-atom parameters constrained
wR(F²) = 0.117	Δρ_max = 0.17 e Å⁻³
S = 0.99	Δρ_min = −0.25 e Å⁻³
5502 reflections	Absolute structure: Flack (1983), 2283 Friedel pairs
268 parameters	Absolute structure parameter: 0.05 (11)
0 restraints

Special details top

Experimental. The intensity data was collected on a Bruker SMART 1 K CCD diffractometer using an exposure time of 20 s/frame. A total of 984 frames were collected with a frame width of 0.3° covering up to θ = 28.37° with 99.3% completeness accomplished.

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
P1	0.60082 (6)	0.44749 (6)	0.87672 (2)	0.03329 (18)
C1	0.4783 (2)	0.4567 (2)	0.84292 (9)	0.0370 (7)
C2	0.4328 (2)	0.3813 (3)	0.81337 (9)	0.0454 (8)
H2	0.4651	0.3126	0.8092	0.054*
C3	0.3384 (3)	0.4104 (3)	0.79028 (11)	0.0576 (9)
H3	0.3082	0.3616	0.7698	0.069*
C4	0.2892 (3)	0.5108 (3)	0.79748 (13)	0.0744 (12)
H4	0.2255	0.5289	0.7819	0.089*
C5	0.3324 (3)	0.5852 (3)	0.82750 (13)	0.0746 (12)
H5	0.2979	0.6525	0.8322	0.09*
C6	0.4280 (2)	0.5587 (3)	0.85057 (10)	0.0472 (8)
C7	0.4846 (2)	0.6282 (2)	0.88434 (10)	0.0450 (7)
C8	0.4517 (3)	0.7307 (3)	0.89949 (13)	0.0692 (11)
H8	0.3888	0.7639	0.888	0.083*
C9	0.5129 (4)	0.7833 (3)	0.93185 (12)	0.0687 (11)
H9	0.4896	0.8516	0.9424	0.082*
C10	0.6074 (3)	0.7372 (3)	0.94885 (10)	0.0536 (9)
H10	0.6475	0.774	0.9706	0.064*
C11	0.6428 (3)	0.6358 (3)	0.93346 (9)	0.0427 (8)
H11	0.7076	0.6048	0.9443	0.051*
C12	0.5808 (2)	0.5806 (2)	0.90172 (9)	0.0359 (7)
C13	0.7242 (2)	0.4477 (3)	0.83999 (9)	0.0402 (7)
C14	0.7210 (3)	0.3492 (3)	0.80819 (11)	0.0714 (12)
H14A	0.7818	0.3538	0.7878	0.107*
H14B	0.653	0.3501	0.7918	0.107*
H14C	0.7262	0.2821	0.8249	0.107*
C15	0.8297 (3)	0.4475 (3)	0.86695 (11)	0.0643 (10)
H15A	0.8327	0.382	0.8848	0.096*
H15B	0.8314	0.5112	0.8859	0.096*
H15C	0.8919	0.4491	0.8472	0.096*
C16	0.7161 (3)	0.5544 (3)	0.81278 (12)	0.0724 (11)
H16A	0.7235	0.6167	0.8322	0.109*
H16B	0.6458	0.5573	0.7981	0.109*
H16C	0.7738	0.5558	0.7909	0.109*
C17	0.5876 (3)	0.3380 (2)	0.91950 (10)	0.0441 (8)
C18	0.6709 (3)	0.3567 (3)	0.95735 (11)	0.0679 (11)
H18A	0.6629	0.2996	0.9792	0.102*
H18B	0.6574	0.4271	0.9709	0.102*
H18C	0.7444	0.3552	0.9455	0.102*
C19	0.6031 (3)	0.2239 (3)	0.89885 (11)	0.0651 (10)
H19A	0.5876	0.1684	0.9207	0.098*
H19B	0.6777	0.2162	0.8887	0.098*
H19C	0.5536	0.2156	0.8742	0.098*
C20	0.4700 (3)	0.3478 (3)	0.93813 (13)	0.0797 (13)
H20A	0.4177	0.3361	0.9146	0.12*
H20B	0.4596	0.42	0.9505	0.12*
H20C	0.4592	0.2934	0.9609	0.12*
C21	0.1201 (3)	0.5421 (4)	0.93747 (13)	0.0681 (11)
S1	0.01008 (7)	0.49559 (7)	0.97325 (2)	0.0494 (2)
O1	−0.0109 (2)	0.3861 (2)	0.95856 (8)	0.0773 (8)
O2	0.0560 (2)	0.5059 (2)	1.01687 (8)	0.0780 (8)
O3	−0.0772 (2)	0.5722 (2)	0.96379 (8)	0.0762 (8)
F1	0.0927 (2)	0.5358 (2)	0.89479 (7)	0.0956 (8)
F2	0.2088 (2)	0.4800 (3)	0.94266 (10)	0.1323 (12)
F3	0.1493 (2)	0.6442 (2)	0.94525 (9)	0.1194 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0327 (4)	0.0315 (4)	0.0357 (4)	0.0012 (3)	−0.0020 (3)	−0.0017 (3)
C1	0.0316 (17)	0.0394 (17)	0.0402 (17)	−0.0015 (13)	−0.0040 (12)	−0.0074 (13)
C2	0.0408 (19)	0.046 (2)	0.0499 (18)	−0.0048 (14)	−0.0006 (14)	−0.0101 (14)
C3	0.043 (2)	0.073 (3)	0.057 (2)	−0.0074 (19)	−0.0131 (16)	−0.0140 (19)
C4	0.054 (2)	0.082 (3)	0.087 (3)	0.016 (2)	−0.036 (2)	−0.019 (2)
C5	0.059 (3)	0.068 (3)	0.097 (3)	0.025 (2)	−0.031 (2)	−0.023 (2)
C6	0.0405 (19)	0.0486 (19)	0.0527 (19)	0.0085 (15)	−0.0091 (14)	−0.0083 (16)
C7	0.0429 (19)	0.0394 (18)	0.0527 (19)	0.0092 (14)	−0.0024 (14)	−0.0075 (14)
C8	0.076 (3)	0.052 (2)	0.080 (3)	0.028 (2)	−0.016 (2)	−0.0170 (19)
C9	0.089 (3)	0.043 (2)	0.074 (3)	0.015 (2)	−0.001 (2)	−0.0187 (18)
C10	0.074 (3)	0.044 (2)	0.0424 (19)	−0.0093 (19)	0.0009 (18)	−0.0068 (15)
C11	0.0457 (19)	0.0417 (19)	0.0406 (18)	−0.0064 (15)	−0.0008 (14)	−0.0039 (14)
C12	0.0392 (18)	0.0305 (17)	0.0379 (16)	−0.0011 (12)	0.0000 (13)	−0.0047 (12)
C13	0.0338 (17)	0.0500 (19)	0.0366 (17)	0.0014 (14)	−0.0006 (13)	−0.0024 (15)
C14	0.062 (3)	0.091 (3)	0.061 (2)	0.004 (2)	0.0162 (19)	−0.030 (2)
C15	0.038 (2)	0.100 (3)	0.055 (2)	0.0045 (19)	−0.0035 (16)	−0.007 (2)
C16	0.059 (2)	0.084 (3)	0.075 (3)	0.001 (2)	0.0156 (19)	0.034 (2)
C17	0.048 (2)	0.0409 (19)	0.0433 (18)	−0.0060 (14)	0.0026 (15)	0.0063 (13)
C18	0.088 (3)	0.061 (2)	0.055 (2)	−0.008 (2)	−0.019 (2)	0.0175 (18)
C19	0.090 (3)	0.042 (2)	0.063 (2)	−0.0063 (19)	−0.011 (2)	0.0065 (17)
C20	0.069 (3)	0.092 (3)	0.078 (3)	−0.004 (2)	0.025 (2)	0.026 (2)
C21	0.065 (3)	0.072 (3)	0.068 (3)	−0.002 (2)	−0.002 (2)	−0.003 (2)
S1	0.0554 (5)	0.0515 (5)	0.0412 (4)	−0.0037 (4)	−0.0034 (4)	−0.0056 (4)
O1	0.103 (2)	0.0526 (16)	0.0761 (17)	−0.0131 (15)	−0.0052 (16)	−0.0034 (13)
O2	0.0889 (19)	0.102 (2)	0.0427 (14)	−0.0036 (16)	−0.0149 (12)	−0.0077 (13)
O3	0.0609 (18)	0.089 (2)	0.0783 (16)	0.0226 (14)	−0.0057 (13)	−0.0149 (15)
F1	0.109 (2)	0.125 (2)	0.0528 (13)	−0.0194 (16)	0.0148 (12)	0.0069 (13)
F2	0.0551 (16)	0.197 (4)	0.145 (2)	0.036 (2)	0.0137 (16)	−0.001 (2)
F3	0.139 (3)	0.092 (2)	0.128 (2)	−0.0655 (18)	0.0139 (19)	−0.0078 (16)

Geometric parameters (Å, º) top

P1—C12	1.798 (3)	C14—H14A	0.96
P1—C1	1.804 (3)	C14—H14B	0.96
P1—C17	1.856 (3)	C14—H14C	0.96
P1—C13	1.860 (3)	C15—H15A	0.96
C1—C2	1.389 (4)	C15—H15B	0.96
C1—C6	1.400 (4)	C15—H15C	0.96
C2—C3	1.384 (4)	C16—H16A	0.96
C2—H2	0.93	C16—H16B	0.96
C3—C4	1.374 (5)	C16—H16C	0.96
C3—H3	0.93	C17—C19	1.529 (4)
C4—C5	1.380 (5)	C17—C20	1.538 (5)
C4—H4	0.93	C17—C18	1.538 (4)
C5—C6	1.388 (4)	C18—H18A	0.96
C5—H5	0.93	C18—H18B	0.96
C6—C7	1.487 (4)	C18—H18C	0.96
C7—C8	1.383 (4)	C19—H19A	0.96
C7—C12	1.403 (4)	C19—H19B	0.96
C8—C9	1.380 (5)	C19—H19C	0.96
C8—H8	0.93	C20—H20A	0.96
C9—C10	1.376 (5)	C20—H20B	0.96
C9—H9	0.93	C20—H20C	0.96
C10—C11	1.382 (4)	C21—F3	1.310 (4)
C10—H10	0.93	C21—F2	1.323 (5)
C11—C12	1.387 (4)	C21—F1	1.327 (4)
C11—H11	0.93	C21—S1	1.805 (4)
C13—C15	1.515 (4)	S1—O1	1.423 (3)
C13—C14	1.531 (4)	S1—O2	1.430 (2)
C13—C16	1.534 (4)	S1—O3	1.438 (2)

C12—P1—C1	93.93 (13)	C13—C14—H14C	109.5
C12—P1—C17	109.98 (13)	H14A—C14—H14C	109.5
C1—P1—C17	111.29 (14)	H14B—C14—H14C	109.5
C12—P1—C13	110.82 (14)	C13—C15—H15A	109.5
C1—P1—C13	109.20 (12)	C13—C15—H15B	109.5
C17—P1—C13	118.82 (14)	H15A—C15—H15B	109.5
C2—C1—C6	120.9 (3)	C13—C15—H15C	109.5
C2—C1—P1	130.3 (2)	H15A—C15—H15C	109.5
C6—C1—P1	108.8 (2)	H15B—C15—H15C	109.5
C3—C2—C1	118.8 (3)	C13—C16—H16A	109.5
C3—C2—H2	120.6	C13—C16—H16B	109.5
C1—C2—H2	120.6	H16A—C16—H16B	109.5
C4—C3—C2	120.4 (3)	C13—C16—H16C	109.5
C4—C3—H3	119.8	H16A—C16—H16C	109.5
C2—C3—H3	119.8	H16B—C16—H16C	109.5
C3—C4—C5	121.2 (3)	C19—C17—C20	109.4 (3)
C3—C4—H4	119.4	C19—C17—C18	110.7 (3)
C5—C4—H4	119.4	C20—C17—C18	109.2 (3)
C4—C5—C6	119.6 (3)	C19—C17—P1	110.9 (2)
C4—C5—H5	120.2	C20—C17—P1	106.1 (2)
C6—C5—H5	120.2	C18—C17—P1	110.5 (2)
C5—C6—C1	119.1 (3)	C17—C18—H18A	109.5
C5—C6—C7	126.6 (3)	C17—C18—H18B	109.5
C1—C6—C7	114.3 (3)	H18A—C18—H18B	109.5
C8—C7—C12	119.1 (3)	C17—C18—H18C	109.5
C8—C7—C6	127.0 (3)	H18A—C18—H18C	109.5
C12—C7—C6	113.9 (3)	H18B—C18—H18C	109.5
C9—C8—C7	119.6 (3)	C17—C19—H19A	109.5
C9—C8—H8	120.2	C17—C19—H19B	109.5
C7—C8—H8	120.2	H19A—C19—H19B	109.5
C10—C9—C8	121.5 (3)	C17—C19—H19C	109.5
C10—C9—H9	119.3	H19A—C19—H19C	109.5
C8—C9—H9	119.3	H19B—C19—H19C	109.5
C9—C10—C11	119.8 (3)	C17—C20—H20A	109.5
C9—C10—H10	120.1	C17—C20—H20B	109.5
C11—C10—H10	120.1	H20A—C20—H20B	109.5
C10—C11—C12	119.4 (3)	C17—C20—H20C	109.5
C10—C11—H11	120.3	H20A—C20—H20C	109.5
C12—C11—H11	120.3	H20B—C20—H20C	109.5
C11—C12—C7	120.6 (3)	F3—C21—F2	107.3 (4)
C11—C12—P1	130.3 (2)	F3—C21—F1	107.1 (3)
C7—C12—P1	109.1 (2)	F2—C21—F1	106.6 (3)
C15—C13—C14	110.7 (3)	F3—C21—S1	112.9 (3)
C15—C13—C16	109.9 (3)	F2—C21—S1	110.7 (3)
C14—C13—C16	108.9 (3)	F1—C21—S1	111.9 (3)
C15—C13—P1	111.3 (2)	O1—S1—O2	115.83 (15)
C14—C13—P1	110.4 (2)	O1—S1—O3	114.24 (17)
C16—C13—P1	105.4 (2)	O2—S1—O3	114.32 (15)
C13—C14—H14A	109.5	O1—S1—C21	103.84 (18)
C13—C14—H14B	109.5	O2—S1—C21	103.35 (17)
H14A—C14—H14B	109.5	O3—S1—C21	103.01 (18)

C12—P1—C1—C2	−178.5 (3)	C17—P1—C12—C11	64.7 (3)
C17—P1—C1—C2	−65.2 (3)	C13—P1—C12—C11	−68.7 (3)
C13—P1—C1—C2	67.9 (3)	C1—P1—C12—C7	−0.2 (2)
C12—P1—C1—C6	1.2 (2)	C17—P1—C12—C7	−114.5 (2)
C17—P1—C1—C6	114.4 (2)	C13—P1—C12—C7	112.1 (2)
C13—P1—C1—C6	−112.5 (2)	C12—P1—C13—C15	74.3 (3)
C6—C1—C2—C3	2.3 (4)	C1—P1—C13—C15	176.4 (2)
P1—C1—C2—C3	−178.1 (2)	C17—P1—C13—C15	−54.5 (3)
C1—C2—C3—C4	−1.8 (5)	C12—P1—C13—C14	−162.4 (2)
C2—C3—C4—C5	0.4 (6)	C1—P1—C13—C14	−60.2 (3)
C3—C4—C5—C6	0.6 (6)	C17—P1—C13—C14	68.8 (3)
C4—C5—C6—C1	−0.1 (6)	C12—P1—C13—C16	−44.9 (2)
C4—C5—C6—C7	−179.1 (4)	C1—P1—C13—C16	57.2 (2)
C2—C1—C6—C5	−1.3 (5)	C17—P1—C13—C16	−173.7 (2)
P1—C1—C6—C5	179.0 (3)	C12—P1—C17—C19	179.3 (2)
C2—C1—C6—C7	177.8 (3)	C1—P1—C17—C19	76.6 (3)
P1—C1—C6—C7	−1.9 (3)	C13—P1—C17—C19	−51.5 (3)
C5—C6—C7—C8	1.2 (6)	C12—P1—C17—C20	60.7 (3)
C1—C6—C7—C8	−177.9 (3)	C1—P1—C17—C20	−42.0 (3)
C5—C6—C7—C12	−179.1 (3)	C13—P1—C17—C20	−170.1 (2)
C1—C6—C7—C12	1.9 (4)	C12—P1—C17—C18	−57.6 (3)
C12—C7—C8—C9	−1.1 (5)	C1—P1—C17—C18	−160.3 (2)
C6—C7—C8—C9	178.6 (3)	C13—P1—C17—C18	71.6 (3)
C7—C8—C9—C10	1.3 (6)	F3—C21—S1—O1	178.2 (3)
C8—C9—C10—C11	0.0 (5)	F2—C21—S1—O1	−61.4 (3)
C9—C10—C11—C12	−1.5 (5)	F1—C21—S1—O1	57.3 (3)
C10—C11—C12—C7	1.8 (4)	F3—C21—S1—O2	−60.5 (3)
C10—C11—C12—P1	−177.4 (2)	F2—C21—S1—O2	59.9 (3)
C8—C7—C12—C11	−0.5 (5)	F1—C21—S1—O2	178.6 (3)
C6—C7—C12—C11	179.8 (3)	F3—C21—S1—O3	58.8 (3)
C8—C7—C12—P1	178.9 (3)	F2—C21—S1—O3	179.2 (3)
C6—C7—C12—P1	−0.9 (3)	F1—C21—S1—O3	−62.1 (3)
C1—P1—C12—C11	179.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.49	3.381 (4)	161
C19—H19A···O2ⁱⁱ	0.96	2.52	3.458 (4)	165
C11—H11···O3ⁱⁱⁱ	0.93	2.7	3.601 (4)	162
C15—H15B···O3ⁱⁱⁱ	0.96	2.69	3.470 (4)	138

Symmetry codes: (i) x+1/2, −y+1/2, −z+7/4; (ii) y, x, −z+2; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₆P⁺·CF₃O₃S⁻
M_r	446.45
Crystal system, space group	Tetragonal, P4₁2₁2
Temperature (K)	293
a, c (Å)	12.1339 (10), 30.057 (2)
V (Å³)	4425.4 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.4 × 0.26 × 0.2

Data collection
Diffractometer	Bruker SMART 1K CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.902, 0.949
No. of measured, independent and observed [I > 2σ(I)] reflections	25275, 5502, 3241
R_int	0.101
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.117, 0.99
No. of reflections	5502
No. of parameters	268
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.25
Absolute structure	Flack (1983), 2283 Friedel pairs
Absolute structure parameter	0.05 (11)

Computer programs: SMART-NT (Bruker, 1998), SAINT-Plus (Bruker, 2008), SAINT-Plus and XPREP (Bruker, 2008), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.49	3.381 (4)	161.4
C19—H19A···O2ⁱⁱ	0.96	2.52	3.458 (4)	165
C11—H11···O3ⁱⁱⁱ	0.93	2.7	3.601 (4)	162
C15—H15B···O3ⁱⁱⁱ	0.96	2.69	3.470 (4)	138.2

Symmetry codes: (i) x+1/2, −y+1/2, −z+7/4; (ii) y, x, −z+2; (iii) x+1, y, z.

Acknowledgements

The University of Witwatersrand is thanked for the use of their diffractometer. The research fund of the University of Johannesburg is gratefully acknowledged.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Beletskaya, I. P. & Cheprakov, A. V. (2004). J. Organomet. Chem. 689, 4055–4082. Web of Science CrossRef CAS Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1998). SMART-NT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2008). SADABS, SAINT-Plus and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Herrman, W. A., Ofele, K., Preysing, D. & Schneider, S. K. (2003). J. Organomet. Chem. 687, 229–248. Google Scholar
Omondi, B., Shaw, M. L. & Holzapfel, C. W. (2011). J. Organomet. Chem. 696, 3091–3096. Web of Science CSD CrossRef CAS Google Scholar
Orlye, E. d' & Jutland, A. (2005). Tetrahedron, 61, 9670–9678. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Williams, D. G. B., Shaw, M. L., Green, M. J. & Holzapfel, C. W. (2008). Angew. Chem. Int. Ed. 47, 560–563. Web of Science CrossRef CAS Google Scholar