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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o445.
Published online 2010 January 27. doi:  10.1107/S1600536810002461
PMCID: PMC2979863

2,2-Dichloro-1-(2-phenyl-1,3-oxazolidin-3-yl)ethanone

Abstract

In the title mol­ecule, C11H11Cl2NO2, the oxazolidine ring is in an envelope conformation with the O atom forming the flap; the other four essentially planar ring atoms (r.m.s. deviation = 0.012 Å) form a dihedral angle of 91.1 (3)° with the phenyl ring. In the crystal structure, mol­ecules are linked by weak inter­molecular C—H(...)O hydrogen bonds, forming one-dimensional chains.

Related literature

For general background to substituted oxazolidines see: Agami et al. (2004 [triangle]); Guirado et al. (2003 [triangle]); Tararov et al. (2003 [triangle]). For the bioactivity of related compounds, see: Hatzios et al. (2004 [triangle]); Daniele et al. (2007 [triangle]). For details of the synthesis, see: Fu et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o445-scheme1.jpg

Experimental

Crystal data

  • C11H11Cl2NO2
  • M r = 260.11
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o445-efi1.jpg
  • a = 19.1775 (13) Å
  • b = 10.6165 (7) Å
  • c = 11.3723 (8) Å
  • V = 2315.4 (3) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.54 mm−1
  • T = 298 K
  • 0.46 × 0.38 × 0.20 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.780, T max = 0.897
  • 16860 measured reflections
  • 2846 independent reflections
  • 2323 reflections with I > 2σ(I)
  • R int = 0.022

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.110
  • S = 1.04
  • 2846 reflections
  • 145 parameters
  • H-atom parameters constrained
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [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.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810002461/lh2978sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002461/lh2978Isup2.hkl

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

Acknowledgments

We thanks the Heilongjiang Province Foundation for Young Scholar (QC2009C44), the China Postdoctoral Science Foundation (20080430951), the Heilongjiang Province Postdoctoral Science Foundation (LBH-Z07012) and the Northeast Agricultural University Doctoral Foundation for generously supporting this study.

supplementary crystallographic information

Comment

Substituted oxazolidines are important synthetic targets due to their biological activity (Agami et al., 2004), pharmacological activity and their extensive use as chiral auxiliaries for the synthesis of many chiral compounds (Guirado et al., 2003; Tararov et al. 2003). Dichloroacetemide compounds have been shown to act as herbicide safeners (Hatzios, 2004; Daniele et al., 2007). As part of our ongoing investigations of oxazolidine derivatives we prepared the title compound and its crystal structure is reported herein.

The molecular structure of the title compound is shown in Fig.1. In the crystal structure, molecules are linked by weak intermolecular C—H···O hydrogen bonds to form one-dimensional chains (Fig. 2).

Experimental

The title compound was prepared by a slightly modified literature procedure (Fu et al., 2009).

Ethanolamine (4.1 g, 0.067 mol) and 7.1g (0.067mol) of benzaldehyde were mixed with 25mL of benzene. The reaction mixture was stirred for 1h at 306-308K. Then, the mixture was heated to reflux and water was evaporated, followed by cooling to 273K and 7.5 mL of 33% sodium hydroxide solution was added. 11.8 g (0.08mol) of dichloroacetyl chloride was added dropwise with stirring, keeping the temperature at 273-277K. Stirring was continued for 1.5h. The mixture was rinsed with water until the pH=7. The organic phase was dried over anhydrous magnesium sulfate and the benzene was removed under vacuum. The crude product was recrystallized with ethyl acetate and light petroleum, white crystals wre obtained. The yield was 58.2%. m.p. 374-377K.

The single-crystal suitable for X-ray structural analysis was obtained by slow evaporation of a solution of the title compound in petroleum ether and ethyl acetate at room temperature.

Refinement

All H atoms were initially located in a difference Fourier map. The C—H atoms were then constrained to an ideal geometry, with C-H = 0.93 - 0.98Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound, with the atom-labelling scheme.Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
Part of the crystal structure of the title compound showing C-H···O hydrogen bonds as dashed lines.

Crystal data

C11H11Cl2NO2F(000) = 1072.0
Mr = 260.11Dx = 1.492 Mg m3Dm = 1.492 Mg m3Dm measured by not measured
Orthorhombic, PccnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2acCell parameters from 5877 reflections
a = 19.1775 (13) Åθ = 2.8–27.9°
b = 10.6165 (7) ŵ = 0.54 mm1
c = 11.3723 (8) ÅT = 298 K
V = 2315.4 (3) Å3Block, colourless
Z = 80.46 × 0.38 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer2846 independent reflections
Radiation source: fine-focus sealed tube2323 reflections with I > 2σ(I)
graphiteRint = 0.022
[var phi] and ω scansθmax = 28.3°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −25→25
Tmin = 0.780, Tmax = 0.897k = −14→14
16860 measured reflectionsl = −15→15

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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0473P)2 + 1.2513P] where P = (Fo2 + 2Fc2)/3
2846 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = −0.29 e Å3

Special details

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)

xyzUiso*/Ueq
Cl10.43189 (3)0.78273 (5)0.61104 (4)0.05385 (16)
Cl20.38622 (3)0.67345 (6)0.83020 (5)0.06457 (19)
N10.54978 (8)0.77484 (13)0.88700 (13)0.0370 (3)
O10.60625 (8)0.77362 (14)1.06154 (12)0.0555 (4)
C110.46001 (9)0.72103 (16)0.74626 (16)0.0398 (4)
H110.49040.64830.73230.048*
C100.49952 (9)0.82044 (15)0.81777 (15)0.0372 (4)
O20.48479 (8)0.93204 (12)0.81157 (14)0.0554 (4)
C90.56836 (10)0.64244 (17)0.90877 (18)0.0468 (4)
H9A0.58820.60340.83930.056*
H9B0.52830.59400.93470.056*
C50.65059 (10)0.91874 (17)0.91330 (18)0.0469 (4)
C70.58735 (10)0.85716 (17)0.96905 (16)0.0431 (4)
H70.55570.92210.99920.052*
C60.67948 (11)0.8764 (2)0.8089 (2)0.0549 (5)
H60.65880.80940.76960.066*
C80.62234 (13)0.65601 (19)1.0063 (2)0.0593 (6)
H8A0.61870.58721.06200.071*
H8B0.66920.65710.97410.071*
C10.73902 (12)0.9323 (2)0.7616 (3)0.0722 (7)
H10.75790.90270.69150.087*
C20.76916 (14)1.0306 (3)0.8190 (3)0.0880 (10)
H20.80871.06840.78730.106*
C30.74266 (15)1.0743 (2)0.9217 (3)0.0859 (10)
H30.76441.14080.96020.103*
C40.68205 (13)1.0194 (2)0.9706 (3)0.0687 (7)
H40.66351.05031.04040.082*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0541 (3)0.0720 (4)0.0354 (2)−0.0010 (2)−0.00397 (19)0.0028 (2)
Cl20.0712 (4)0.0745 (4)0.0481 (3)−0.0336 (3)0.0014 (2)0.0033 (2)
N10.0418 (7)0.0300 (7)0.0392 (8)0.0004 (5)−0.0036 (6)−0.0011 (6)
O10.0760 (9)0.0524 (8)0.0380 (7)0.0039 (7)−0.0131 (7)0.0019 (6)
C110.0440 (9)0.0380 (9)0.0374 (9)0.0004 (7)−0.0043 (7)−0.0017 (7)
C100.0404 (8)0.0332 (8)0.0379 (9)−0.0010 (7)−0.0017 (7)0.0010 (7)
O20.0669 (9)0.0311 (6)0.0684 (9)0.0031 (6)−0.0216 (7)0.0007 (6)
C90.0557 (11)0.0333 (9)0.0513 (11)0.0084 (8)−0.0050 (9)−0.0002 (7)
C50.0479 (10)0.0323 (8)0.0604 (12)0.0007 (7)−0.0221 (9)0.0043 (8)
C70.0518 (10)0.0380 (9)0.0394 (9)0.0051 (8)−0.0115 (8)−0.0054 (7)
C60.0491 (10)0.0543 (12)0.0614 (13)−0.0079 (9)−0.0096 (9)0.0089 (10)
C80.0771 (14)0.0455 (11)0.0552 (12)0.0101 (10)−0.0184 (11)0.0056 (9)
C10.0502 (12)0.0794 (16)0.0871 (18)−0.0083 (12)−0.0058 (12)0.0259 (14)
C20.0569 (14)0.0697 (17)0.138 (3)−0.0160 (13)−0.0268 (17)0.0369 (19)
C30.0719 (16)0.0409 (11)0.145 (3)−0.0149 (11)−0.0536 (19)0.0079 (15)
C40.0716 (14)0.0397 (10)0.0948 (18)0.0036 (10)−0.0389 (14)−0.0066 (11)

Geometric parameters (Å, °)

Cl1—C111.7563 (18)C5—C41.389 (3)
Cl2—C111.7803 (19)C5—C71.517 (3)
N1—C101.335 (2)C7—H70.9800
N1—C71.468 (2)C6—C11.395 (3)
N1—C91.471 (2)C6—H60.9300
O1—C71.423 (2)C8—H8A0.9700
O1—C81.431 (3)C8—H8B0.9700
C11—C101.533 (2)C1—C21.360 (4)
C11—H110.9800C1—H10.9300
C10—O21.220 (2)C2—C31.355 (5)
C9—C81.524 (3)C2—H20.9300
C9—H9A0.9700C3—C41.414 (4)
C9—H9B0.9700C3—H30.9300
C5—C61.385 (3)C4—H40.9300
C10—N1—C7120.89 (14)O1—C7—H7109.7
C10—N1—C9128.35 (15)N1—C7—H7109.7
C7—N1—C9110.07 (14)C5—C7—H7109.7
C7—O1—C8105.92 (14)C5—C6—C1121.4 (2)
C10—C11—Cl1111.07 (12)C5—C6—H6119.3
C10—C11—Cl2107.69 (12)C1—C6—H6119.3
Cl1—C11—Cl2109.34 (10)O1—C8—C9104.80 (16)
C10—C11—H11109.6O1—C8—H8A110.8
Cl1—C11—H11109.6C9—C8—H8A110.8
Cl2—C11—H11109.6O1—C8—H8B110.8
O2—C10—N1123.59 (16)C9—C8—H8B110.8
O2—C10—C11121.57 (16)H8A—C8—H8B108.9
N1—C10—C11114.83 (14)C2—C1—C6119.2 (3)
N1—C9—C8101.35 (15)C2—C1—H1120.4
N1—C9—H9A111.5C6—C1—H1120.4
C8—C9—H9A111.5C3—C2—C1121.2 (3)
N1—C9—H9B111.5C3—C2—H2119.4
C8—C9—H9B111.5C1—C2—H2119.4
H9A—C9—H9B109.3C2—C3—C4120.4 (2)
C6—C5—C4118.5 (2)C2—C3—H3119.8
C6—C5—C7122.59 (17)C4—C3—H3119.8
C4—C5—C7118.9 (2)C5—C4—C3119.3 (3)
O1—C7—N1102.94 (14)C5—C4—H4120.3
O1—C7—C5111.96 (15)C3—C4—H4120.3
N1—C7—C5112.55 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C11—H11···O2i0.982.403.312 (2)156

Symmetry codes: (i) −x+1, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2978).

References

  • Agami, C. & Couty, F. (2004). Eur. J. Org. Chem.69, 677–685.
  • Bruker (1998). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Daniele, D. B., Luciano, S. & Luca, E. (2007). Phytochemistry, 68, 2614–2618.
  • Fu, Y., Fu, H. G., Ye, F., Mao, J. D. & Wen, X. T. (2009). Synth. Commun.39, 2454–2463.
  • Guirado, A., Andreu, R. & Galvez, J. (2003). Tetrahedron Lett.44, 3809–3841.
  • Hatzios, K. K. (2004). Weed Sci.52, 454–467.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Tararov, V. I., Kadyrov, R., Monsees, A., Riermeier, T. H. & Boerner, A. (2003). Adv. Synth. Catal.345, 239–245.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography