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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2922.
Published online 2009 October 31. doi:  10.1107/S1600536809044067
PMCID: PMC2971319

Dimethyl (2-hydr­oxy-4-phenyl­but-3-en-2-yl)phospho­nate

Abstract

In the title compound, C12H17O4P, the phenyl­butenyl group is disordered over two sets of sites with an occupancy ratio of 0.755 (12):0.245 (12). In the crystal, inversion dimers linked by pairs of O—H(...)O hydrogen bonds occur, forming R 2 2(10) ring motifs. The packing is consolidated by weak C—H(...)π inter­actions.

Related literature

For related structures, see: Acar et al. (2009 [triangle]); Tahir et al. (2007 [triangle], 2009a [triangle],b [triangle]). For graph-set theory, see: Bernstein et al. (1995 [triangle]).

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Object name is e-65-o2922-scheme1.jpg

Experimental

Crystal data

  • C12H17O4P
  • M r = 256.23
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2922-efi1.jpg
  • a = 17.1522 (12) Å
  • b = 8.1571 (13) Å
  • c = 19.5230 (12) Å
  • β = 103.771 (10)°
  • V = 2653.0 (5) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.21 mm−1
  • T = 296 K
  • 0.25 × 0.14 × 0.12 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (MolEN; Fair, 1990 [triangle]) T min = 0.885, T max = 0.954
  • 2519 measured reflections
  • 2415 independent reflections
  • 1684 reflections with I > 2σ(I)
  • R int = 0.095
  • 3 standard reflections frequency: 120 min intensity decay: 0.6%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.061
  • wR(F 2) = 0.175
  • S = 1.07
  • 2415 reflections
  • 177 parameters
  • H-atom parameters constrained
  • Δρmax = 0.53 e Å−3
  • Δρmin = −0.42 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1993 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990 [triangle]); program(s) used to solve structure: WinGX (Farrugia, 1999 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044067/hb5172sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044067/hb5172Isup2.hkl

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

supplementary crystallographic information

Comment

We have reported the crystal structures which contains α-hydroxy phosphonate such as (II) Dimethyl (1-hydroxy-1,2-diphenylethyl)phosphonate (Tahir et al., 2009a), (III) Dimethyl [hydroxy(2-nitrophenyl)methyl]phosphonate (Tahir et al., 2009b), (IV) (R)-Dimethyl [(2-chlorophenyl)hydroxymethyl]phosphonate (Tahir et al., 2007) and Diethyl (1-hydroxy-1,2-diphenylethyl)phosphonate (Acar et al., 2009). The title compound (I, Fig. 1) is in continuation of synthesizing various α-hydroxy phosphonates.

In the crystal structure of title compound phenylbutan is disordered over two possible sites with occupancy ratio of 0.755 (12):0.245 (12). The benzene rings of disordered moieties A (C1A—C6A) and B (C1B—C6B) are nearly planar to one another as the dihedral angle between A/B is 2.76 (1.35)°. The molecules of title compound are dimerized due to O—H···O type of intermolecular H-bondings (Table 1, Fig. 3) forming R22(10) ring motif (Bernstein et al., 1995). The molecules are stabilized due to C–H···π interactions (Table 1).

Experimental

Benzylacetone (4.45 g, 30 mmol) and dimethylphosphonate (3.30 g, 30 mmol) were dissolved in 50 ml of tetrahydrofuran. The mixture was cooled to 273 K and in it KF (1.74 g, 30 mmol) and γ-Al2O3 (1.74 g, 17 mmol) were added and refluxed. The precipitates obtained after 48 h were washed with hot distiled water (50 ml) and dried. The crude material was dissolved in distiled water with few drops of ethyl alcohol and colourless needles of (I) were obtained after 4 days.

Refinement

The H-atoms were positioned geometrically (O–H = 0.82 Å, C–H = 0.93-0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl C).

The incorrect bond distances and higher thermal parameters of phenylbutan lead to disorder. In the disordered group the benzene rings were refined using AFIX 66. The benzene ring B (C2B—C6B) was refined using EADP.

Figures

Fig. 1.
View of (I) with the atom numbering scheme for atoms of greater occupancy ratio. The displacement ellipsoids are drawn at the 30% probability level. H-atoms are shown by small circles of arbitrary radii.
Fig. 2.
View of the title compound with the atom numbering scheme for atoms of smaller occupancy ratio. The displacement ellipsoids are drawn at the 30% probability level. H-atoms are shown by small circles of arbitrary radii.
Fig. 3.
The partial packing of (I), which shows that molecules form inversion dimers.

Crystal data

C12H17O4PF(000) = 1088
Mr = 256.23Dx = 1.283 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 17.1522 (12) Åθ = 9.9–13.9°
b = 8.1571 (13) ŵ = 0.21 mm1
c = 19.5230 (12) ÅT = 296 K
β = 103.771 (10)°Needle, colourless
V = 2653.0 (5) Å30.25 × 0.14 × 0.12 mm
Z = 8

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.095
ω/2θ scansθmax = 25.5°, θmin = 2.8°
Absorption correction: ψ scan (MolEN; Fair, 1990)h = −20→20
Tmin = 0.885, Tmax = 0.954k = 0→9
2519 measured reflectionsl = −23→0
2415 independent reflections3 standard reflections every 120 min
1684 reflections with I > 2σ(I) intensity decay: 0.6%

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.175w = 1/[σ2(Fo2) + (0.114P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
2415 reflectionsΔρmax = 0.53 e Å3
177 parametersΔρmin = −0.42 e Å3
0 restraints

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

xyzUiso*/UeqOcc. (<1)
P10.43961 (4)0.29251 (9)0.06739 (4)0.0399 (3)
O10.43699 (13)0.6068 (3)0.08493 (11)0.0548 (8)
O20.49603 (12)0.2946 (3)0.02130 (12)0.0528 (8)
O30.37510 (12)0.1526 (2)0.05085 (11)0.0500 (7)
O40.48115 (13)0.2636 (3)0.14713 (12)0.0597 (8)
C1A0.2124 (3)0.4228 (6)0.1674 (2)0.0453 (16)0.755 (12)
C2A0.23963 (19)0.4970 (7)0.2329 (3)0.058 (2)0.755 (12)
C3A0.1939 (3)0.4884 (9)0.28271 (18)0.078 (2)0.755 (12)
C4A0.1209 (3)0.4058 (9)0.2671 (3)0.072 (2)0.755 (12)
C5A0.0937 (2)0.3316 (6)0.2017 (3)0.062 (2)0.755 (12)
C6A0.1395 (3)0.3401 (6)0.15183 (15)0.0524 (17)0.755 (12)
C7A0.2601 (3)0.4283 (6)0.1139 (2)0.0451 (16)0.755 (12)
C8A0.3344 (4)0.4814 (7)0.1215 (3)0.0414 (19)0.755 (12)
C90.37966 (18)0.4799 (3)0.06310 (16)0.0440 (10)
C100.3323 (2)0.5090 (4)−0.01138 (18)0.0584 (11)
C110.4001 (2)−0.0152 (4)0.0447 (2)0.0644 (13)
C120.5626 (2)0.3125 (6)0.1775 (2)0.0896 (19)
C6B0.1066 (9)0.341 (2)0.1847 (9)0.061 (3)0.245 (12)
C7B0.3065 (12)0.441 (2)0.0916 (13)0.046 (6)0.245 (12)
C1B0.1670 (11)0.380 (2)0.1509 (5)0.061 (3)0.245 (12)
C2B0.2328 (8)0.471 (2)0.1857 (9)0.061 (3)0.245 (12)
C3B0.2381 (8)0.525 (2)0.2543 (9)0.061 (3)0.245 (12)
C4B0.1777 (12)0.486 (3)0.2880 (7)0.061 (3)0.245 (12)
C5B0.1119 (10)0.395 (3)0.2532 (9)0.061 (3)0.245 (12)
C8B0.2981 (10)0.5086 (19)0.1470 (10)0.057 (6)0.245 (12)
H10.457060.631430.052180.0821*
H2A0.288440.552260.243310.0697*0.755 (12)
H10C0.368120.51292−0.042330.0875*
H11A0.35594−0.087620.044460.0966*
H11B0.41720−0.027950.001650.0966*
H11C0.44381−0.041170.084030.0966*
H12A0.597640.261870.152020.1344*
H12B0.566930.429500.174850.1344*
H12C0.577620.278620.225980.1344*
H3A0.212030.538060.326500.0928*0.755 (12)
H4A0.090260.400080.300470.0865*0.755 (12)
H5A0.044890.276300.191240.0741*0.755 (12)
H6A0.121300.290500.108040.0629*0.755 (12)
H7A0.234850.389560.069320.0541*0.755 (12)
H8A0.360860.522420.165320.0500*0.755 (12)
H10A0.294440.42147−0.025550.0875*
H10B0.303980.61121−0.013710.0875*
H1B0.163420.343690.105030.0729*0.245 (12)
H3B0.282130.586350.277580.0729*0.245 (12)
H4B0.181260.522180.333910.0729*0.245 (12)
H5B0.071470.368760.275800.0729*0.245 (12)
H6B0.062550.279510.161360.0729*0.245 (12)
H7B0.268150.366540.068050.0543*0.245 (12)
H8B0.335140.589220.166260.0680*0.245 (12)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0354 (4)0.0436 (5)0.0463 (5)0.0019 (3)0.0206 (3)0.0024 (3)
O10.0676 (15)0.0482 (12)0.0568 (13)−0.0064 (11)0.0312 (12)−0.0074 (10)
O20.0520 (13)0.0542 (13)0.0644 (14)0.0030 (10)0.0382 (11)0.0013 (10)
O30.0399 (12)0.0423 (11)0.0723 (15)0.0011 (9)0.0225 (10)−0.0003 (10)
O40.0499 (13)0.0785 (15)0.0530 (14)0.0069 (12)0.0167 (11)0.0118 (11)
C1A0.037 (3)0.064 (3)0.036 (2)0.007 (2)0.011 (2)−0.005 (2)
C2A0.043 (3)0.093 (4)0.045 (4)−0.002 (2)0.022 (2)−0.011 (3)
C3A0.055 (4)0.140 (5)0.047 (3)−0.025 (4)0.031 (3)−0.022 (3)
C4A0.053 (4)0.121 (5)0.051 (3)−0.013 (3)0.029 (3)−0.020 (3)
C5A0.046 (3)0.096 (4)0.054 (4)0.000 (2)0.033 (2)−0.008 (3)
C6A0.035 (3)0.078 (3)0.051 (3)−0.002 (2)0.024 (2)−0.007 (2)
C7A0.040 (3)0.061 (3)0.040 (2)−0.007 (2)0.021 (2)−0.011 (2)
C8A0.038 (4)0.047 (3)0.040 (3)0.002 (2)0.011 (3)−0.005 (2)
C90.0388 (16)0.0440 (16)0.0560 (18)0.0029 (13)0.0245 (14)0.0051 (13)
C100.051 (2)0.0560 (19)0.069 (2)0.0017 (15)0.0160 (17)0.0091 (16)
C110.066 (2)0.0462 (18)0.085 (3)0.0049 (16)0.026 (2)−0.0011 (16)
C120.065 (3)0.119 (4)0.074 (3)−0.015 (2)−0.005 (2)−0.003 (2)
C6B0.037 (4)0.112 (7)0.040 (5)−0.002 (4)0.024 (3)−0.003 (4)
C7B0.034 (10)0.047 (9)0.058 (13)0.003 (7)0.015 (9)0.002 (7)
C1B0.037 (4)0.112 (7)0.040 (5)−0.002 (4)0.024 (3)−0.003 (4)
C2B0.037 (4)0.112 (7)0.040 (5)−0.002 (4)0.024 (3)−0.003 (4)
C3B0.037 (4)0.112 (7)0.040 (5)−0.002 (4)0.024 (3)−0.003 (4)
C4B0.037 (4)0.112 (7)0.040 (5)−0.002 (4)0.024 (3)−0.003 (4)
C5B0.037 (4)0.112 (7)0.040 (5)−0.002 (4)0.024 (3)−0.003 (4)
C8B0.036 (8)0.056 (9)0.083 (12)−0.010 (7)0.023 (9)−0.028 (8)

Geometric parameters (Å, °)

P1—O21.470 (2)C8A—C91.525 (7)
P1—O31.569 (2)C9—C101.506 (5)
P1—O41.568 (2)C1B—H1B0.9300
P1—C91.833 (3)C2A—H2A0.9300
O1—C91.422 (4)C3A—H3A0.9300
O3—C111.448 (4)C3B—H3B0.9300
O4—C121.438 (4)C4A—H4A0.9300
O1—H10.8200C4B—H4B0.9300
C1A—C2A1.391 (7)C5A—H5A0.9300
C1A—C7A1.473 (7)C5B—H5B0.9300
C1A—C6A1.389 (7)C6A—H6A0.9300
C1B—C2B1.39 (2)C6B—H6B0.9300
C1B—C6B1.39 (2)C7A—H7A0.9300
C2A—C3A1.389 (6)C7B—H7B0.9300
C2B—C8B1.52 (2)C8A—H8A0.9300
C2B—C3B1.39 (2)C8B—H8B0.9300
C3A—C4A1.390 (8)C10—H10B0.9600
C3B—C4B1.39 (2)C10—H10A0.9600
C4A—C5A1.390 (8)C10—H10C0.9600
C4B—C5B1.39 (3)C11—H11A0.9600
C5A—C6A1.391 (6)C11—H11B0.9600
C5B—C6B1.39 (2)C11—H11C0.9600
C7A—C8A1.321 (9)C12—H12A0.9600
C7B—C8B1.25 (3)C12—H12B0.9600
C7B—C91.52 (2)C12—H12C0.9600
O2—P1—O3114.66 (13)C2A—C3A—H3A120.00
O2—P1—O4113.56 (13)C4A—C3A—H3A120.00
O2—P1—C9113.97 (14)C2B—C3B—H3B120.00
O3—P1—O4103.09 (12)C4B—C3B—H3B120.00
O3—P1—C9103.70 (12)C3A—C4A—H4A120.00
O4—P1—C9106.75 (14)C5A—C4A—H4A120.00
P1—O3—C11119.8 (2)C3B—C4B—H4B120.00
P1—O4—C12122.3 (2)C5B—C4B—H4B120.00
C9—O1—H1109.00C4A—C5A—H5A120.00
C2A—C1A—C7A121.1 (4)C6A—C5A—H5A120.00
C6A—C1A—C7A118.9 (4)C4B—C5B—H5B120.00
C2A—C1A—C6A120.0 (4)C6B—C5B—H5B120.00
C2B—C1B—C6B120.1 (12)C5A—C6A—H6A120.00
C1A—C2A—C3A120.0 (4)C1A—C6A—H6A120.00
C1B—C2B—C3B120.0 (14)C1B—C6B—H6B120.00
C1B—C2B—C8B118.3 (14)C5B—C6B—H6B120.00
C3B—C2B—C8B121.7 (14)C1A—C7A—H7A116.00
C2A—C3A—C4A120.0 (5)C8A—C7A—H7A116.00
C2B—C3B—C4B119.8 (15)C9—C7B—H7B120.00
C3A—C4A—C5A120.0 (5)C8B—C7B—H7B120.00
C3B—C4B—C5B120.2 (15)C7A—C8A—H8A118.00
C4A—C5A—C6A120.0 (4)C9—C8A—H8A118.00
C4B—C5B—C6B120.0 (16)C2B—C8B—H8B117.00
C1A—C6A—C5A120.0 (4)C7B—C8B—H8B117.00
C1B—C6B—C5B119.9 (15)C9—C10—H10C110.00
C1A—C7A—C8A127.9 (4)C9—C10—H10B109.00
C8B—C7B—C9119.9 (17)C9—C10—H10A109.00
C7A—C8A—C9124.3 (5)H10B—C10—H10C109.00
C2B—C8B—C7B126.1 (17)H10A—C10—H10B109.00
C7B—C9—C1094.8 (9)H10A—C10—H10C110.00
O1—C9—C10110.5 (2)H11A—C11—H11B110.00
O1—C9—C7B127.9 (8)O3—C11—H11A109.00
C8A—C9—C10117.9 (3)O3—C11—H11B109.00
P1—C9—O1104.7 (2)O3—C11—H11C109.00
P1—C9—C8A110.6 (3)H11A—C11—H11C109.00
P1—C9—C10110.1 (2)H11B—C11—H11C109.00
P1—C9—C7B108.2 (7)H12B—C12—H12C109.00
O1—C9—C8A102.1 (3)O4—C12—H12A109.00
C2B—C1B—H1B120.00O4—C12—H12B109.00
C6B—C1B—H1B120.00O4—C12—H12C109.00
C1A—C2A—H2A120.00H12A—C12—H12B110.00
C3A—C2A—H2A120.00H12A—C12—H12C109.00
O2—P1—O3—C1150.8 (3)C6A—C1A—C2A—C3A0.0 (8)
O4—P1—O3—C11−73.1 (2)C7A—C1A—C2A—C3A−179.3 (5)
C9—P1—O3—C11175.7 (2)C2A—C1A—C6A—C5A0.1 (7)
O2—P1—O4—C1228.4 (3)C7A—C1A—C6A—C5A179.3 (4)
O3—P1—O4—C12153.1 (3)C2A—C1A—C7A—C8A8.7 (8)
C9—P1—O4—C12−98.0 (3)C6A—C1A—C7A—C8A−170.6 (5)
O2—P1—C9—O1−60.4 (2)C1A—C2A—C3A—C4A−0.1 (9)
O2—P1—C9—C8A−169.6 (3)C2A—C3A—C4A—C5A0.1 (10)
O2—P1—C9—C1058.4 (3)C3A—C4A—C5A—C6A−0.1 (9)
O3—P1—C9—O1174.29 (18)C4A—C5A—C6A—C1A0.0 (8)
O3—P1—C9—C8A65.1 (3)C1A—C7A—C8A—C9179.0 (4)
O3—P1—C9—C10−67.0 (2)C7A—C8A—C9—P1−93.6 (6)
O4—P1—C9—O165.8 (2)C7A—C8A—C9—O1155.5 (5)
O4—P1—C9—C8A−43.4 (3)C7A—C8A—C9—C1034.2 (7)
O4—P1—C9—C10−175.4 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O2i0.821.902.721 (3)176
C6B—H6B···Cg1ii0.932.833.568 (17)137
C6B—H6B···Cg2ii0.932.943.652 (17)134

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1/2, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5172).

References

  • Acar, N., Tahir, M. N., Tariq, R. H. & Yilmaz, H. (2009). Acta Cryst. E65, o1203. [PMC free article] [PubMed]
  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Enraf–Nonius (1993). CAD-4 EXPRESS Enraf–Nonius, Delft, The Netherlands.
  • Fair, C. K. (1990). MolEN Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Tahir, M. N., Acar, N., Yilmaz, H., Danish, M. & Ülkü, D. (2007). Acta Cryst. E63, o3817–o3818.
  • Tahir, M. N., Acar, N., Yilmaz, H. & Tariq, R. H. (2009b). Acta Cryst. E65, o2051. [PMC free article] [PubMed]
  • Tahir, M. N., Acar, N., Yilmaz, H., Tariq, M. I. & Ülkü, D. (2009a). Acta Cryst. E65, o562. [PMC free article] [PubMed]

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