(Biphenyl-2,2'-di-yl)di-tert-butyl-phos-phonium trifluoro-methane-sulfonate.

To aid in the elucidation of catalytic reaction mechanism of palladacycles, we found that reaction of trifluoro-methane-sulfonic 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 tetra-hedral P-atom environment with biphen-yl-P-biphenyl = 93.93 (13)° and t-Bu-P-t-Bu = 118.82 (14)°. In the crystal, weak C-H⋯O inter-actions 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 = 446.45

Tetragonal,

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[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.117

S = 0.99

5502 reflections

268 parameters

H-atom parameters constrained

Δρmax = 0.17 e Å−3

Δρmin = −0.25 e Å−3

Absolute structure: Flack (1983 ▶), 2283 Friedel pairs

Flack parameter: 0.05 (11)

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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812049045/aa2079sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812049045/aa2079Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C20H26P+·CF3O3S−	Dx = 1.34 Mg m−3
Mr = 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

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

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(Fo2) + (0.0519P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max = 0.001
5502 reflections	Δρmax = 0.17 e Å−3
268 parameters	Δρmin = −0.25 e Å−3
0 restraints	Absolute structure: Flack (1983), 2283 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.05 (11)

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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

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) ; (ii) ; (iii) .