organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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(SP)-Menthyl benzyl­(phenyl)­phospho­nate

aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
*Correspondence e-mail: literabc@hotmail.com

(Received 9 March 2010; accepted 12 March 2010; online 17 March 2010)

The title compound, C23H31O2P, has three fully extended substituents around the P-atom chiral centre, forming an SP 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[Dilworth, J. R. & Wheatley, N. (2000). Coord. Chem. Rev. 199, 89-158.]); Chae et al. (1994[Chae, M. Y., Postula, J. F. & Raushel, F. M. (1994). Bioorg. Med. Chem. Lett. 4, 1473-1478.]). For alkyl­ates of phospho­rus-sulfur compounds, see: Aitken (2005[Aitken, R. A. (2005). Comprehensive Organic Functional Group Transformations II, pp. 539-573. Amsterdam:Elsevier]).

[Scheme 1]

Experimental

Crystal data
  • C23H31O2P

  • Mr = 370.45

  • Monoclinic, P 21

  • 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.943, Tmax = 0.986

  • 5541 measured reflections

  • 3576 independent reflections

  • 2596 reflections with I > 2σ(I)

  • Rint = 0.085

Refinement
  • R[F2 > 2σ(F2)] = 0.066

  • wR(F2) = 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[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 1432 Friedel pairs

  • Flack parameter: −0.17 (16)

Data collection: SMART (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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.

Related literature top

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

Experimental top

(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 top

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.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the compound. H atoms have been omitted for clarity.
(SP)-Menthyl benzyl(phenyl)phosphonate top
Crystal data top
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 top
Siemens SMART CCD area-detector
diffractometer
3576 independent reflections
Radiation source: fine-focus sealed tube2596 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.085
phi and ω scansθmax = 25.0°, θmin = 1.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1414
Tmin = 0.943, Tmax = 0.986k = 66
5541 measured reflectionsl = 1518
Refinement top
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) = 0.170 w = 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 methodsAbsolute structure parameter: 0.17 (16)
Crystal data top
C23H31O2PV = 1095.8 (2) Å3
Mr = 370.45Z = 2
Monoclinic, P21Mo Kα radiation
a = 12.4777 (11) ŵ = 0.14 mm1
b = 5.7970 (7) ÅT = 298 K
c = 15.4190 (19) Å0.43 × 0.11 × 0.10 mm
β = 100.727 (1)°
Data collection top
Siemens SMART CCD area-detector
diffractometer
3576 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2596 reflections with I > 2σ(I)
Tmin = 0.943, Tmax = 0.986Rint = 0.085
5541 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.170Δρmax = 0.28 e Å3
S = 0.89Δρmin = 0.23 e Å3
3576 reflectionsAbsolute structure: Flack (1983), 1432 Friedel pairs
238 parametersAbsolute structure parameter: 0.17 (16)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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)
H120.21670.52000.02040.074*
C130.3260 (4)0.3096 (13)0.0641 (3)0.0790 (15)
H130.33870.40500.10970.095*
C140.3790 (4)0.1029 (11)0.0502 (4)0.0762 (15)
H140.42770.05810.08590.091*
C150.3601 (4)0.0387 (11)0.0170 (4)0.0776 (15)
H150.39640.17910.02670.093*
C160.2876 (4)0.0258 (9)0.0701 (3)0.0652 (13)
H160.27440.07240.11460.078*
C170.0306 (3)0.1248 (8)0.1089 (3)0.0511 (10)
H17A0.01100.14790.04980.061*
H17B0.06030.03030.11170.061*
C180.0457 (3)0.1452 (8)0.1747 (3)0.0490 (10)
C190.1144 (4)0.3305 (10)0.1742 (3)0.0668 (12)
H190.11530.44780.13290.080*
C200.1828 (4)0.3417 (13)0.2360 (4)0.0828 (16)
H200.22840.46840.23630.099*
C210.1837 (5)0.1675 (13)0.2966 (4)0.0861 (18)
H210.23020.17520.33710.103*
C220.1159 (5)0.0153 (12)0.2966 (4)0.0910 (19)
H220.11550.13240.33790.109*
C230.0479 (4)0.0298 (10)0.2365 (3)0.0689 (13)
H230.00280.15760.23690.083*
Atomic displacement parameters (Å2) top
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, º) top
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, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O10.982.492.893 (5)104

Experimental details

Crystal data
Chemical formulaC23H31O2P
Mr370.45
Crystal system, space groupMonoclinic, P21
Temperature (K)298
a, b, c (Å)12.4777 (11), 5.7970 (7), 15.4190 (19)
β (°) 100.727 (1)
V3)1095.8 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.14
Crystal size (mm)0.43 × 0.11 × 0.10
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.943, 0.986
No. of measured, independent and
observed [I > 2σ(I)] reflections
5541, 3576, 2596
Rint0.085
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.066, 0.170, 0.89
No. of reflections3576
No. of parameters238
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.23
Absolute structureFlack (1983), 1432 Friedel pairs
Absolute structure parameter0.17 (16)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
P1—O21.470 (3)P1—C171.796 (4)
P1—O11.595 (3)P1—C111.814 (4)
O2—P1—O1114.13 (15)O2—P1—C11112.96 (18)
O2—P1—C17115.1 (2)O1—P1—C11105.23 (17)
O1—P1—C17102.76 (18)C17—P1—C11105.6 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O10.982.492.893 (5)104
 

Acknowledgements

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

References

First citationAitken, R. A. (2005). Comprehensive Organic Functional Group Transformations II, pp. 539–573. Amsterdam:Elsevier  CrossRef Google Scholar
First citationChae, M. Y., Postula, J. F. & Raushel, F. M. (1994). Bioorg. Med. Chem. Lett. 4, 1473–1478.  CrossRef CAS Web of Science Google Scholar
First citationDilworth, J. R. & Wheatley, N. (2000). Coord. Chem. Rev. 199, 89–158.  Web of Science CrossRef CAS Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSiemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.  Google Scholar

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