Tri-p-tolyl­phosphine

Wang, H.; Wang, Y.-B.; Liu, B.-N.; Tang, S.-G.; Wei, P.

doi:10.1107/S160053680802374X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 9| September 2008| Page o1783

doi:10.1107/S160053680802374X

Open

access

Tri-p-tolylphosphine

Hao Wang,^a Yi-Bin Wang,^a Bo-Nian Liu,^b Shi-Gui Tang ^a and Ping Wei ^a ^*

^aCollege of Life Sciences And Pharmaceutical Engineering, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bCollege of Science, Nanjing University of Technolgy, Xinmofan Road No.5, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 3 June 2008; accepted 27 July 2008; online 20 August 2008)

In the title compound C₂₁H₂₁P, the P atom is situated on a crystallographic threefold rotatory-inversion axis, resulting in threefold rotation symmetry of the title compound. The dihedral angles between the symmetry-related benzene rings are 87.40 (18)°.

Related literature

For related literature, see: Brown et al. (1988 ).

Experimental

Crystal data

C₂₁H₂₁P
M_r = 304.35
Trigonal, $[R \overline 3]$
a = 12.6562 (18) Å
c = 19.696 (4) Å
V = 2732.2 (8) Å³
Z = 6
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 (2) K
0.40 × 0.30 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.958, T_max = 0.971
3464 measured reflections
1095 independent reflections
790 reflections with I > 2σ(I)
R_int = 0.050
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.171
S = 1.03
1095 reflections
67 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680802374X/kj2091sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680802374X/kj2091Isup2.hkl

checkCIF report

Comment top

Some organophosphorus derivatives are important chemical materials, which are primarily used as intermediates of organic phosphorus flame retardants and phosphorus ligands in biphasic water soluble catalysts. The P atom is situated on a crystallographic threefold rotatory-inversion axis, resulting in threefold rotation symmetry of the title compound.

The dihedral angles between the symmetry-related benzene rings are 87.40 (18)°.

Related literature top

For related literature, see: Brown et al. (1988).

Experimental top

20 g Sodium (0.870 mol) was added to 125 ml toluene, then the mixture was heated up to 383 K and stirred to form fine particles of sodium, which subsequently melted. Then the temperature was lowered to 323 K. P-chlorotoluene (55.2 g / 0.436 mol) and phosphorus trichloride (19.8 g / 0.144 mol) were added, keeping the temperature between 323 K and 333 K for two hours. The product was concentrated in a vacuum to gain a white solid (35.0 g, 80%) (Brown et al., 1988). The pure title compound was obtained by crystallizing from methanol. Crystals suitable for X-ray diffraction were obtained by slow evaporation of an methanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level. Symmetry codes: (i) 1 - x + y,1 - x,z (ii) 1 - y + 1,x-y,z

(I) top

Crystal data top

C₂₁H₂₁P	D_x = 1.110 Mg m⁻³
M_r = 304.35	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 25 reflections
Hall symbol: -R 3	θ = 10–13°
a = 12.6562 (18) Å	µ = 0.15 mm⁻¹
c = 19.696 (4) Å	T = 293 K
V = 2732.2 (8) Å³	Block, colourless
Z = 6	0.40 × 0.30 × 0.20 mm
F(000) = 972

Data collection top

Enraf–Nonius CAD-4 diffractometer	790 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 25.2°, θ_min = 2.1°
ω/2θ scans	h = −15→7
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
T_min = 0.958, T_max = 0.971	l = 0→23
3464 measured reflections	3 standard reflections every 200 reflections
1095 independent reflections	intensity decay: none

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.171	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.05P)² + 4P] where P = (F_o² + 2F_c²)/3
1095 reflections	(Δ/σ)_max < 0.001
67 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₂₁H₂₁P	Z = 6
M_r = 304.35	Mo Kα radiation
Trigonal, R3	µ = 0.15 mm⁻¹
a = 12.6562 (18) Å	T = 293 K
c = 19.696 (4) Å	0.40 × 0.30 × 0.20 mm
V = 2732.2 (8) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	790 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.050
T_min = 0.958, T_max = 0.971	3 standard reflections every 200 reflections
3464 measured reflections	intensity decay: none
1095 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.171	H-atom parameters constrained
S = 1.03	Δρ_max = 0.26 e Å⁻³
1095 reflections	Δρ_min = −0.34 e Å⁻³
67 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
P	0.6667	0.3333	0.01046 (7)	0.0705 (5)
C1	0.8153 (4)	0.8316 (3)	−0.1198 (2)	0.0992 (12)
H1A	0.7776	0.8686	−0.0944	0.149*
H1B	0.7882	0.8209	−0.1661	0.149*
H1C	0.9024	0.8832	−0.1182	0.149*
C2	0.7805 (3)	0.7091 (3)	−0.08924 (18)	0.0710 (8)
C3	0.8232 (3)	0.6365 (3)	−0.11520 (14)	0.0647 (8)
H3A	0.8752	0.6636	−0.1525	0.078*
C4	0.7903 (3)	0.5238 (3)	−0.08689 (15)	0.0644 (7)
H4A	0.8205	0.4768	−0.1058	0.077*
C5	0.7147 (3)	0.4803 (2)	−0.03192 (14)	0.0609 (7)
C6	0.6732 (3)	0.5549 (3)	−0.0040 (2)	0.0811 (10)
H6A	0.6247	0.5301	0.0348	0.097*
C7	0.7050 (3)	0.6663 (3)	−0.03445 (19)	0.0809 (10)
H7A	0.6735	0.7130	−0.0167	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P	0.0791 (6)	0.0791 (6)	0.0533 (8)	0.0396 (3)	0.000	0.000
C1	0.096 (3)	0.076 (2)	0.128 (4)	0.044 (2)	0.000 (2)	0.008 (2)
C2	0.0533 (16)	0.0599 (17)	0.097 (2)	0.0259 (14)	−0.0093 (15)	−0.0109 (16)
C3	0.0609 (16)	0.0699 (18)	0.0587 (17)	0.0294 (14)	0.0003 (13)	−0.0060 (13)
C4	0.0648 (17)	0.0653 (17)	0.0666 (18)	0.0353 (14)	−0.0009 (14)	−0.0129 (14)
C5	0.0607 (16)	0.0677 (17)	0.0530 (16)	0.0312 (13)	−0.0028 (12)	−0.0109 (13)
C6	0.069 (2)	0.083 (2)	0.091 (2)	0.0377 (17)	0.0151 (17)	−0.0131 (18)
C7	0.074 (2)	0.076 (2)	0.100 (3)	0.0436 (17)	0.0036 (18)	−0.0164 (18)

Geometric parameters (Å, º) top

P—C5ⁱ	1.843 (3)	C3—C4	1.388 (4)
P—C5ⁱⁱ	1.843 (3)	C3—H3A	0.9300
P—C5	1.843 (3)	C4—C5	1.366 (4)
C1—C2	1.508 (4)	C4—H4A	0.9300
C1—H1A	0.9600	C5—C6	1.401 (4)
C1—H1B	0.9600	C6—C7	1.394 (5)
C1—H1C	0.9600	C6—H6A	0.9300
C2—C7	1.361 (5)	C7—H7A	0.9300
C2—C3	1.377 (4)

C5ⁱ—P—C5ⁱⁱ	101.08 (11)	C4—C3—H3A	119.3
C5ⁱ—P—C5	101.08 (11)	C5—C4—C3	121.5 (3)
C5ⁱⁱ—P—C5	101.08 (11)	C5—C4—H4A	119.3
C2—C1—H1A	109.5	C3—C4—H4A	119.3
C2—C1—H1B	109.5	C4—C5—C6	117.6 (3)
H1A—C1—H1B	109.5	C4—C5—P	125.2 (2)
C2—C1—H1C	109.5	C6—C5—P	117.1 (2)
H1A—C1—H1C	109.5	C7—C6—C5	119.8 (3)
H1B—C1—H1C	109.5	C7—C6—H6A	120.1
C7—C2—C3	117.4 (3)	C5—C6—H6A	120.1
C7—C2—C1	120.8 (3)	C2—C7—C6	122.3 (3)
C3—C2—C1	121.8 (3)	C2—C7—H7A	118.8
C2—C3—C4	121.4 (3)	C6—C7—H7A	118.8
C2—C3—H3A	119.3

C7—C2—C3—C4	0.3 (5)	C5ⁱ—P—C5—C6	−169.0 (2)
C1—C2—C3—C4	−179.8 (3)	C5ⁱⁱ—P—C5—C6	87.2 (3)
C2—C3—C4—C5	−0.3 (5)	C4—C5—C6—C7	3.0 (5)
C3—C4—C5—C6	−1.4 (5)	P—C5—C6—C7	−179.0 (3)
C3—C4—C5—P	−179.2 (2)	C3—C2—C7—C6	1.5 (5)
C5ⁱ—P—C5—C4	8.8 (3)	C1—C2—C7—C6	−178.4 (3)
C5ⁱⁱ—P—C5—C4	−95.0 (2)	C5—C6—C7—C2	−3.2 (5)

Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −y+1, x−y, z.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₁P
M_r	304.35
Crystal system, space group	Trigonal, R3
Temperature (K)	293
a, c (Å)	12.6562 (18), 19.696 (4)
V (Å³)	2732.2 (8)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.958, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	3464, 1095, 790
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.171, 1.03
No. of reflections	1095
No. of parameters	67
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.34

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

Brown, S. J., Clark, J. H. & Macquarrie, D. J. (1988). J. Chem. Soc. Dalton Trans. pp. 277–80. CrossRef Web of Science Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef 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