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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o863.
Published online 2010 March 17. doi:  10.1107/S1600536810009372
PMCID: PMC2984029

(S P)-Menthyl benzyl­(phenyl)­phospho­nate

Abstract

The title compound, C23H31O2P, has three fully extended substituents around the P-atom chiral centre, forming an S P configuration. The phenyl rings are inclined at a dihedral angle of 3.2 (3)°.

Related literature

For general background to phospho­rus-sulfur compounds, see: Dilworth & Wheatley (2000 [triangle]); Chae et al. (1994 [triangle]). For alkyl­ates of phospho­rus-sulfur compounds, see: Aitken (2005 [triangle]).

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Object name is e-66-0o863-scheme1.jpg

Experimental

Crystal data

  • C23H31O2P
  • M r = 370.45
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o863-efi1.jpg
  • a = 12.4777 (11) Å
  • b = 5.7970 (7) Å
  • c = 15.4190 (19) Å
  • β = 100.727 (1)°
  • V = 1095.8 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.14 mm−1
  • T = 298 K
  • 0.43 × 0.11 × 0.10 mm

Data collection

  • Siemens SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.943, T max = 0.986
  • 5541 measured reflections
  • 3576 independent reflections
  • 2596 reflections with I > 2σ(I)
  • R int = 0.085

Refinement

  • R[F 2 > 2σ(F 2)] = 0.066
  • wR(F 2) = 0.170
  • S = 0.89
  • 3576 reflections
  • 238 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.23 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1432 Friedel pairs
  • Flack parameter: −0.17 (16)

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810009372/bx2269sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810009372/bx2269Isup2.hkl

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

Acknowledgments

We acknowledge the financial support of the Natural Science Foundation of China (No. 20772055).

supplementary crystallographic information

Comment

Phosphorus-sulfur compounds, especially P-chiral, have extensive applications (Dilworth et al. 2000; Chae et al. 1994), wherein their alkylates are of significant senes, for example, they usually act as common ligands (Aitken et al. 2005). The title compound is a P-chiral compounds, which can be synthesized by (Rp)-O-menthyl S-ethyl phenylphosphonothioate and benzylmagnesium chloride. The compound is comprised of fully extended substituents: phenyl, menthyloxy and benzyl, and O atom which form a irregular tetrahedron, (Table 1). The phenyl rings makes a dihedral angle of 3.2 (3)°.The six-membered menthyloxy ring is in a chair conformation. The molecular structure is stabilized by a intramolecular C—H··· O hydrogen bond [C···O =2.893 (5) Å , C—H··· O =104°]. There are no further significant intermolecular interactions.

Experimental

(Rp)-O-menthyl S-ethyl phenylphosphonothioate (0.3 mmol) was added to a stirred ether solution of benzylmagnesium chloride (0.6 mmol) in a Schlenk tube under nitrogen and the mixture was stirred for 24 h at room temperature. After washing with water, the resulting solution was purified by silica gel plate to afford optically pure product. The crystal suitable for X-ray diffraction was obtained from recrystallization with ethyl ether/hexane.

Refinement

All H atoms attached to C atoms were fixed geometrically and treated as riding with C—H = 0.93-0.98 Å, with Uiso(H) = 1.5 Ueq(methyl) and Uiso(H) = 1.2 Ueq(C) for all other H atoms.

Figures

Fig. 1.
The molecular structure of the compound. H atoms have been omitted for clarity.

Crystal data

C23H31O2PF(000) = 400
Mr = 370.45Dx = 1.123 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 1629 reflections
a = 12.4777 (11) Åθ = 2.7–25.0°
b = 5.7970 (7) ŵ = 0.14 mm1
c = 15.4190 (19) ÅT = 298 K
β = 100.727 (1)°Block, colorless
V = 1095.8 (2) Å30.43 × 0.11 × 0.10 mm
Z = 2

Data collection

Siemens SMART CCD area-detector diffractometer3576 independent reflections
Radiation source: fine-focus sealed tube2596 reflections with I > 2σ(I)
graphiteRint = 0.085
phi and ω scansθmax = 25.0°, θmin = 1.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −14→14
Tmin = 0.943, Tmax = 0.986k = −6→6
5541 measured reflectionsl = −15→18

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.170w = 1/[σ2(Fo2) + (0.1052P)2] where P = (Fo2 + 2Fc2)/3
S = 0.89(Δ/σ)max < 0.001
3576 reflectionsΔρmax = 0.28 e Å3
238 parametersΔρmin = −0.23 e Å3
1 restraintAbsolute structure: Flack (1983), 1432 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.17 (16)

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

xyzUiso*/Ueq
P10.14134 (8)0.32764 (18)0.12780 (6)0.0440 (3)
O10.2011 (2)0.2676 (5)0.22583 (18)0.0495 (7)
O20.1092 (2)0.5709 (5)0.11455 (18)0.0539 (8)
C10.2811 (3)0.3635 (8)0.3776 (3)0.0513 (11)
H10.33160.23270.38100.062*
C20.2606 (3)0.4484 (9)0.2817 (3)0.0494 (10)
H20.21400.58560.27760.059*
C30.3653 (4)0.5136 (9)0.2527 (3)0.0604 (13)
H3A0.34920.56510.19180.072*
H3B0.41190.37880.25560.072*
C40.4259 (4)0.7041 (10)0.3099 (3)0.0736 (15)
H40.37760.83870.30450.088*
C50.4456 (4)0.6286 (13)0.4061 (3)0.0831 (17)
H5A0.49640.50040.41420.100*
H5B0.47860.75480.44300.100*
C60.3419 (4)0.5571 (10)0.4352 (3)0.0694 (14)
H6A0.29420.69010.43290.083*
H6B0.35900.50490.49590.083*
C70.1778 (4)0.2749 (10)0.4090 (3)0.0665 (14)
H70.14550.15540.36720.080*
C80.0910 (5)0.4614 (15)0.4086 (4)0.104 (2)
H8A0.02680.39380.42390.157*
H8B0.07310.52860.35080.157*
H8C0.11870.57870.45080.157*
C90.2060 (5)0.1607 (12)0.4997 (3)0.0865 (18)
H9A0.23170.27560.54350.130*
H9B0.26200.04720.49920.130*
H9C0.14220.08760.51340.130*
C100.5316 (5)0.7791 (15)0.2790 (4)0.113 (3)
H10A0.58120.65110.28380.170*
H10B0.56490.90370.31530.170*
H10C0.51430.82890.21860.170*
C110.2347 (3)0.2350 (7)0.0575 (3)0.0445 (10)
C120.2528 (4)0.3793 (9)−0.0106 (3)0.0615 (14)
H120.21670.5200−0.02040.074*
C130.3260 (4)0.3096 (13)−0.0641 (3)0.0790 (15)
H130.33870.4050−0.10970.095*
C140.3790 (4)0.1029 (11)−0.0502 (4)0.0762 (15)
H140.42770.0581−0.08590.091*
C150.3601 (4)−0.0387 (11)0.0170 (4)0.0776 (15)
H150.3964−0.17910.02670.093*
C160.2876 (4)0.0258 (9)0.0701 (3)0.0652 (13)
H160.2744−0.07240.11460.078*
C170.0306 (3)0.1248 (8)0.1089 (3)0.0511 (10)
H17A−0.01100.14790.04980.061*
H17B0.0603−0.03030.11170.061*
C18−0.0457 (3)0.1452 (8)0.1747 (3)0.0490 (10)
C19−0.1144 (4)0.3305 (10)0.1742 (3)0.0668 (12)
H19−0.11530.44780.13290.080*
C20−0.1828 (4)0.3417 (13)0.2360 (4)0.0828 (16)
H20−0.22840.46840.23630.099*
C21−0.1837 (5)0.1675 (13)0.2966 (4)0.0861 (18)
H21−0.23020.17520.33710.103*
C22−0.1159 (5)−0.0153 (12)0.2966 (4)0.0910 (19)
H22−0.1155−0.13240.33790.109*
C23−0.0479 (4)−0.0298 (10)0.2365 (3)0.0689 (13)
H23−0.0028−0.15760.23690.083*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0524 (5)0.0365 (6)0.0430 (5)0.0020 (6)0.0084 (4)−0.0002 (5)
O10.0601 (16)0.0395 (19)0.0464 (15)0.0000 (13)0.0034 (12)−0.0034 (12)
O20.0638 (16)0.0401 (18)0.0577 (18)0.0061 (15)0.0106 (14)−0.0018 (13)
C10.054 (2)0.055 (3)0.044 (2)0.005 (2)0.0090 (17)−0.002 (2)
C20.052 (2)0.048 (3)0.047 (2)0.003 (2)0.0061 (19)−0.008 (2)
C30.067 (3)0.068 (4)0.047 (2)−0.007 (2)0.012 (2)0.000 (2)
C40.069 (3)0.087 (4)0.064 (3)−0.018 (3)0.009 (2)−0.013 (3)
C50.074 (3)0.114 (5)0.058 (3)−0.023 (3)0.004 (2)−0.015 (3)
C60.066 (3)0.090 (4)0.052 (3)−0.009 (3)0.011 (2)−0.014 (3)
C70.078 (3)0.078 (4)0.047 (2)−0.008 (3)0.022 (2)−0.005 (2)
C80.075 (3)0.136 (6)0.107 (5)0.023 (4)0.031 (3)0.026 (4)
C90.111 (4)0.089 (5)0.067 (4)−0.004 (4)0.036 (3)0.001 (3)
C100.101 (4)0.152 (8)0.089 (4)−0.061 (5)0.022 (3)−0.019 (5)
C110.047 (2)0.042 (3)0.044 (2)−0.0032 (18)0.0047 (17)0.0013 (17)
C120.067 (3)0.062 (4)0.058 (3)0.002 (2)0.017 (2)0.006 (2)
C130.088 (3)0.091 (4)0.066 (3)−0.005 (4)0.034 (3)0.006 (4)
C140.070 (3)0.080 (4)0.087 (4)−0.008 (3)0.037 (3)−0.020 (3)
C150.075 (3)0.058 (3)0.107 (4)0.010 (3)0.032 (3)−0.007 (3)
C160.070 (3)0.056 (3)0.075 (3)0.008 (3)0.029 (3)0.008 (2)
C170.057 (2)0.046 (3)0.049 (2)0.004 (2)0.0082 (19)−0.0035 (19)
C180.055 (2)0.043 (3)0.048 (2)−0.005 (2)0.0085 (18)−0.0033 (19)
C190.070 (3)0.056 (3)0.076 (3)0.010 (3)0.017 (2)0.009 (3)
C200.069 (3)0.084 (4)0.100 (4)0.003 (3)0.028 (3)−0.013 (4)
C210.078 (4)0.103 (5)0.088 (4)−0.013 (4)0.041 (3)−0.007 (4)
C220.112 (5)0.088 (5)0.082 (4)−0.012 (4)0.042 (3)0.018 (4)
C230.085 (3)0.053 (3)0.072 (3)−0.002 (3)0.025 (3)0.013 (3)

Geometric parameters (Å, °)

P1—O21.470 (3)C9—H9C0.9600
P1—O11.595 (3)C10—H10A0.9600
P1—C171.796 (4)C10—H10B0.9600
P1—C111.814 (4)C10—H10C0.9600
O1—C21.467 (5)C11—C161.377 (6)
C1—C21.533 (5)C11—C121.394 (6)
C1—C61.540 (6)C12—C131.400 (7)
C1—C71.548 (6)C12—H120.9300
C1—H10.9800C13—C141.366 (8)
C2—C31.507 (6)C13—H130.9300
C2—H20.9800C14—C151.377 (8)
C3—C41.524 (7)C14—H140.9300
C3—H3A0.9700C15—C161.380 (7)
C3—H3B0.9700C15—H150.9300
C4—C51.522 (7)C16—H160.9300
C4—C101.546 (7)C17—C181.519 (6)
C4—H40.9800C17—H17A0.9700
C5—C61.504 (7)C17—H17B0.9700
C5—H5A0.9700C18—C191.374 (6)
C5—H5B0.9700C18—C231.396 (6)
C6—H6A0.9700C19—C201.395 (7)
C6—H6B0.9700C19—H190.9300
C7—C81.529 (8)C20—C211.377 (9)
C7—C91.528 (7)C20—H200.9300
C7—H70.9800C21—C221.356 (9)
C8—H8A0.9600C21—H210.9300
C8—H8B0.9600C22—C231.370 (7)
C8—H8C0.9600C22—H220.9300
C9—H9A0.9600C23—H230.9300
C9—H9B0.9600
O2—P1—O1114.13 (15)C7—C9—H9A109.5
O2—P1—C17115.1 (2)C7—C9—H9B109.5
O1—P1—C17102.76 (18)H9A—C9—H9B109.5
O2—P1—C11112.96 (18)C7—C9—H9C109.5
O1—P1—C11105.23 (17)H9A—C9—H9C109.5
C17—P1—C11105.6 (2)H9B—C9—H9C109.5
C2—O1—P1119.8 (3)C4—C10—H10A109.5
C2—C1—C6107.3 (4)C4—C10—H10B109.5
C2—C1—C7114.1 (3)H10A—C10—H10B109.5
C6—C1—C7114.2 (4)C4—C10—H10C109.5
C2—C1—H1106.9H10A—C10—H10C109.5
C6—C1—H1106.9H10B—C10—H10C109.5
C7—C1—H1106.9C16—C11—C12119.6 (4)
O1—C2—C3112.1 (3)C16—C11—P1121.4 (3)
O1—C2—C1108.2 (4)C12—C11—P1119.0 (3)
C3—C2—C1111.6 (3)C11—C12—C13119.1 (5)
O1—C2—H2108.3C11—C12—H12120.5
C3—C2—H2108.3C13—C12—H12120.5
C1—C2—H2108.3C14—C13—C12120.7 (5)
C2—C3—C4111.9 (4)C14—C13—H13119.7
C2—C3—H3A109.2C12—C13—H13119.7
C4—C3—H3A109.2C13—C14—C15119.7 (5)
C2—C3—H3B109.2C13—C14—H14120.2
C4—C3—H3B109.2C15—C14—H14120.2
H3A—C3—H3B107.9C14—C15—C16120.5 (6)
C5—C4—C3109.2 (5)C14—C15—H15119.7
C5—C4—C10112.9 (4)C16—C15—H15119.7
C3—C4—C10112.6 (5)C11—C16—C15120.4 (5)
C5—C4—H4107.3C11—C16—H16119.8
C3—C4—H4107.3C15—C16—H16119.8
C10—C4—H4107.3C18—C17—P1113.5 (3)
C6—C5—C4112.2 (4)C18—C17—H17A108.9
C6—C5—H5A109.2P1—C17—H17A108.9
C4—C5—H5A109.2C18—C17—H17B108.9
C6—C5—H5B109.2P1—C17—H17B108.9
C4—C5—H5B109.2H17A—C17—H17B107.7
H5A—C5—H5B107.9C19—C18—C23118.7 (4)
C5—C6—C1112.8 (4)C19—C18—C17121.7 (4)
C5—C6—H6A109.0C23—C18—C17119.6 (4)
C1—C6—H6A109.0C18—C19—C20119.6 (5)
C5—C6—H6B109.0C18—C19—H19120.2
C1—C6—H6B109.0C20—C19—H19120.2
H6A—C6—H6B107.8C21—C20—C19120.9 (6)
C8—C7—C9110.6 (4)C21—C20—H20119.6
C8—C7—C1113.2 (5)C19—C20—H20119.6
C9—C7—C1111.5 (4)C22—C21—C20119.3 (5)
C8—C7—H7107.0C22—C21—H21120.4
C9—C7—H7107.0C20—C21—H21120.4
C1—C7—H7107.0C21—C22—C23120.8 (5)
C7—C8—H8A109.5C21—C22—H22119.6
C7—C8—H8B109.5C23—C22—H22119.6
H8A—C8—H8B109.5C22—C23—C18120.7 (5)
C7—C8—H8C109.5C22—C23—H23119.6
H8A—C8—H8C109.5C18—C23—H23119.6
H8B—C8—H8C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C7—H7···O10.982.492.893 (5)104

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BX2269).

References

  • Aitken, R. A. (2005). Comprehensive Organic Functional Group Transformations II, pp. 539–573. Amsterdam:Elsevier
  • Chae, M. Y., Postula, J. F. & Raushel, F. M. (1994). Bioorg. Med. Chem. Lett.4, 1473–1478.
  • Dilworth, J. R. & Wheatley, N. (2000). Coord. Chem. Rev.199, 89–158.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

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