Acta Cryst. (2008). E64, o1783 [ doi:10.1107/S160053680802374X ]
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)°.
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.
All H atoms bonded to the C atoms were placed geometrically at the distances of 0.93–0.97 Å, and included in the refinement in riding motion approximation with Uiso(H) = 1.2 or 1.5 Ueq of the carrier atom.
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).
![[Figure 1]](./kj2091fig1thm.gif)
| 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 |
| C21H21P | Z = 6 |
| Mr = 304.35 | F000 = 972 |
| Trigonal, R3 | Dx = 1.110 Mg m−3 |
| Hall symbol: -R 3 | Mo Kα radiation λ = 0.71073 Å |
| a = 12.6562 (18) Å | Cell parameters from 25 reflections |
| b = 12.6562 (18) Å | θ = 10–13º |
| c = 19.696 (4) Å | µ = 0.15 mm−1 |
| α = 90º | T = 293 (2) K |
| β = 90º | Block, colourless |
| γ = 120º | 0.40 × 0.30 × 0.20 mm |
| V = 2732.2 (8) Å3 |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.050 |
| Radiation source: fine-focus sealed tube | θmax = 25.2º |
| Monochromator: graphite | θmin = 2.1º |
| T = 293(2) K | h = −15→7 |
| ω/2θ scans | k = 0→15 |
| Absorption correction: ψ scan (North et al., 1968) | l = 0→23 |
| Tmin = 0.958, Tmax = 0.971 | 3 standard reflections |
| 3464 measured reflections | every 200 reflections |
| 1095 independent reflections | intensity decay: none |
| 790 reflections with I > 2σ(I) |
| 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)] = 0.063 | H-atom parameters constrained |
| wR(F2) = 0.171 | w = 1/[σ2(Fo2) + (0.05P)2 + 4P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 1095 reflections | Δρmax = 0.26 e Å−3 |
| 67 parameters | Δρmin = −0.34 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C21H21P | γ = 120º |
| Mr = 304.35 | V = 2732.2 (8) Å3 |
| Trigonal, R3 | Z = 6 |
| a = 12.6562 (18) Å | Mo Kα |
| b = 12.6562 (18) Å | µ = 0.15 mm−1 |
| c = 19.696 (4) Å | T = 293 (2) K |
| α = 90º | 0.40 × 0.30 × 0.20 mm |
| β = 90º |
| Enraf–Nonius CAD-4 diffractometer | 790 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (North et al., 1968) | Rint = 0.050 |
| Tmin = 0.958, Tmax = 0.971 | 3 standard reflections |
| 3464 measured reflections | every 200 reflections |
| 1095 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.063 | 67 parameters |
| wR(F2) = 0.171 | H-atom parameters constrained |
| S = 1.03 | Δρmax = 0.26 e Å−3 |
| 1095 reflections | Δρmin = −0.34 e Å−3 |
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 | ||
| 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* |
| 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) |
| 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. |
The authors thank the Center of Testing and Analysis, Nanjing University, for support.
Brown, S. J., Clark, J. H. & Macquarrie, D. J. (1988). J. Chem. Soc. Dalton Trans. pp. 277–80.
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
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)°.