supplementary materials


lr2037 scheme

Acta Cryst. (2012). E68, o4    [ doi:10.1107/S1600536811051014 ]

(Z)-Methyl 3-(2,4-dichlorophenyl)-3-hydroxyacrylate

L.-X. Xu, X.-G. Bai, J.-X. Wang and Y.-C. Wang

Abstract top

The molecular structure of the title compound, C10H8Cl2O3, exists in a cis-enol form, which is stabilized by a strong intramolecular O-H...O hydrogen bond. In the crystal, C-H...O interactions generate zigzag chains along the c axis which are, in turn, linked by further C-H...O interactions into sheets parallel to (100).

Comment top

1,3-Diketones are versatile intermediates for the synthesis of some palladium(II) and platinum(II) compounds (Nakamoto et al., 1970) and other coordination compounds (Ma et al., 1999; Yoshida et al., 2005). We present here the structure characterization of (Z)-methyl 3-(2,4-dichlorophenyl)-3-hydroxyacrylate.

The molecular structure (Fig.1) exists in a cis-enol form which is stabilized by a strong intramolecular O1—H1···O2 hydrogen bond. The crystal structure (Fig.2) is stabilized by intermolecular C—H···O interactions (Table 1) . The C3—H3···O2 interactions generated zigzag chains along the c axis which in turn are linked by C10—H10B···O1 interactions giving sheets parallel to (100).

Related literature top

For the synthesis of the title compound, see: Wu et al. (1997). For related structures, see: Mei & Huang (2007); Zheng, Fan et al. (2007); Zheng, Zheng et al. (2007). For the coordination properties of similar compounds, see: Nakamoto et al. (1970); Ma et al. (1999); Yoshida et al.(2005).

Experimental top

The title compound was synthesized according to the literature procedure of Wu et al. (1997).Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethanol solution at room temperature.

Refinement top

All H atoms were detected in a difference map, but all other H-atoms were placed in calculated positions and refined using a riding motion approximation, with C—H=0.93–0.96 Å, with Uiso(H)=1.2 or 1.5Ueq(C); O—H=0.82 Å, with Uiso(H)=1.5Ueq(O).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed along the b axis. Hydrogen bonds are shown as dashed lines.
(Z)-Methyl 3-(2,4-dichlorophenyl)-3-hydroxyacrylate top
Crystal data top
C10H8Cl2O3F(000) = 504
Mr = 247.06Dx = 1.562 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 5046 reflections
a = 15.889 (3) Åθ = 3.3–27.0°
b = 3.8242 (8) ŵ = 0.60 mm1
c = 18.204 (4) ÅT = 294 K
β = 108.18 (3)°Prism, colorless
V = 1050.9 (4) Å30.25 × 0.20 × 0.15 mm
Z = 4
Data collection top
Rigaku SCXmini
diffractometer
2170 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.030
graphiteθmax = 27.5°, θmin = 4.1°
Detector resolution: 13.6612 pixels mm-1h = 2020
CCD_Profile_fitting scansk = 44
5011 measured reflectionsl = 2323
2371 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.034 w = 1/[σ2(Fo2) + (0.0413P)2 + 0.0839P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.086(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.17 e Å3
2371 reflectionsΔρmin = 0.18 e Å3
139 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraintsExtinction coefficient: 0.0193 (14)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1177 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.07 (6)
Crystal data top
C10H8Cl2O3V = 1050.9 (4) Å3
Mr = 247.06Z = 4
Monoclinic, CcMo Kα radiation
a = 15.889 (3) ŵ = 0.60 mm1
b = 3.8242 (8) ÅT = 294 K
c = 18.204 (4) Å0.25 × 0.20 × 0.15 mm
β = 108.18 (3)°
Data collection top
Rigaku SCXmini
diffractometer
2170 reflections with I > 2σ(I)
5011 measured reflectionsRint = 0.030
2371 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.086Δρmax = 0.17 e Å3
S = 1.07Δρmin = 0.18 e Å3
2371 reflectionsAbsolute structure: Flack (1983), 1177 Friedel pairs
139 parametersFlack parameter: 0.07 (6)
2 restraints
Special details top

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) top
xyzUiso*/Ueq
C10.58573 (13)0.7958 (6)0.44452 (12)0.0381 (5)
C20.53832 (13)0.7161 (6)0.36792 (12)0.0392 (5)
C30.57482 (16)0.7526 (7)0.30884 (13)0.0439 (5)
H30.54230.69440.25830.053*
C40.65998 (16)0.8762 (6)0.32574 (14)0.0478 (5)
C50.70941 (16)0.9602 (7)0.40023 (15)0.0520 (6)
H50.76691.04470.41090.062*
C60.67267 (16)0.9175 (7)0.45842 (14)0.0495 (6)
H60.70650.97090.50880.059*
C70.55234 (15)0.7569 (6)0.51099 (12)0.0424 (5)
C80.47153 (15)0.8564 (6)0.51265 (13)0.0424 (5)
H80.43150.95480.46890.051*
C90.44659 (15)0.8113 (7)0.58190 (13)0.0441 (5)
C100.3367 (2)0.8937 (8)0.64204 (16)0.0612 (7)
H10A0.33480.65010.65420.092*
H10B0.27870.99340.63190.092*
H10C0.37761.01260.68490.092*
Cl10.43104 (3)0.55059 (16)0.34217 (3)0.05160 (19)
Cl20.70467 (4)0.9249 (2)0.25046 (4)0.0757 (3)
O10.61264 (12)0.6173 (6)0.57216 (10)0.0629 (5)
H10.59310.61200.60880.094*
O20.49301 (12)0.6776 (6)0.64092 (9)0.0620 (5)
O30.36513 (11)0.9310 (5)0.57450 (9)0.0521 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0333 (10)0.0443 (11)0.0353 (10)0.0018 (9)0.0086 (8)0.0022 (8)
C20.0305 (9)0.0449 (12)0.0401 (11)0.0029 (8)0.0081 (8)0.0011 (9)
C30.0384 (10)0.0573 (13)0.0350 (12)0.0029 (10)0.0103 (10)0.0052 (10)
C40.0450 (12)0.0598 (15)0.0441 (12)0.0013 (11)0.0218 (10)0.0021 (11)
C50.0355 (11)0.0657 (15)0.0541 (14)0.0083 (10)0.0130 (11)0.0040 (12)
C60.0368 (12)0.0687 (15)0.0386 (12)0.0056 (11)0.0056 (10)0.0073 (10)
C70.0412 (11)0.0494 (12)0.0329 (11)0.0003 (9)0.0062 (9)0.0009 (9)
C80.0390 (11)0.0525 (13)0.0349 (11)0.0029 (9)0.0104 (9)0.0063 (10)
C90.0423 (12)0.0534 (13)0.0366 (11)0.0007 (10)0.0124 (10)0.0003 (10)
C100.0577 (15)0.083 (2)0.0505 (15)0.0069 (14)0.0281 (13)0.0036 (13)
Cl10.0372 (3)0.0734 (4)0.0422 (3)0.0139 (3)0.0093 (2)0.0054 (3)
Cl20.0592 (4)0.1199 (7)0.0596 (4)0.0099 (5)0.0351 (4)0.0000 (5)
O10.0466 (9)0.1045 (15)0.0347 (9)0.0182 (10)0.0085 (7)0.0137 (9)
O20.0507 (10)0.0981 (14)0.0363 (9)0.0163 (10)0.0124 (8)0.0170 (9)
O30.0434 (8)0.0738 (12)0.0412 (9)0.0096 (8)0.0164 (7)0.0078 (8)
Geometric parameters (Å, °) top
C1—C21.396 (3)C7—O11.333 (3)
C1—C61.404 (3)C7—C81.349 (3)
C1—C71.472 (3)C8—C91.445 (3)
C2—C31.379 (3)C8—H80.9300
C2—Cl11.740 (2)C9—O21.210 (3)
C3—C41.375 (3)C9—O31.340 (3)
C3—H30.9300C10—O31.443 (3)
C4—C51.376 (4)C10—H10A0.9600
C4—Cl21.739 (2)C10—H10B0.9600
C5—C61.370 (3)C10—H10C0.9600
C5—H50.9300O1—H10.8200
C6—H60.9300
C2—C1—C6116.5 (2)O1—C7—C8122.4 (2)
C2—C1—C7125.31 (18)O1—C7—C1112.18 (19)
C6—C1—C7118.17 (19)C8—C7—C1125.4 (2)
C3—C2—C1121.98 (19)C7—C8—C9120.5 (2)
C3—C2—Cl1116.21 (16)C7—C8—H8119.7
C1—C2—Cl1121.77 (16)C9—C8—H8119.7
C4—C3—C2119.0 (2)O2—C9—O3122.4 (2)
C4—C3—H3120.5O2—C9—C8124.6 (2)
C2—C3—H3120.5O3—C9—C8113.00 (19)
C3—C4—C5121.3 (2)O3—C10—H10A109.5
C3—C4—Cl2118.42 (19)O3—C10—H10B109.5
C5—C4—Cl2120.24 (19)H10A—C10—H10B109.5
C6—C5—C4119.0 (2)O3—C10—H10C109.5
C6—C5—H5120.5H10A—C10—H10C109.5
C4—C5—H5120.5H10B—C10—H10C109.5
C5—C6—C1122.2 (2)C7—O1—H1109.5
C5—C6—H6118.9C9—O3—C10115.47 (19)
C1—C6—H6118.9
C6—C1—C2—C30.4 (4)C7—C1—C6—C5179.7 (2)
C7—C1—C2—C3178.6 (2)C2—C1—C7—O1136.9 (2)
C6—C1—C2—Cl1178.08 (18)C6—C1—C7—O142.0 (3)
C7—C1—C2—Cl10.9 (3)C2—C1—C7—C844.8 (3)
C1—C2—C3—C41.0 (4)C6—C1—C7—C8136.3 (3)
Cl1—C2—C3—C4178.9 (2)O1—C7—C8—C90.6 (4)
C2—C3—C4—C50.7 (4)C1—C7—C8—C9178.8 (2)
C2—C3—C4—Cl2179.34 (19)C7—C8—C9—O22.1 (4)
C3—C4—C5—C60.3 (4)C7—C8—C9—O3178.5 (2)
Cl2—C4—C5—C6179.7 (2)O2—C9—O3—C100.7 (4)
C4—C5—C6—C11.0 (4)C8—C9—O3—C10179.9 (2)
C2—C1—C6—C50.7 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O20.821.872.592 (3)146.
C3—H3···O2i0.932.483.356 (3)157.
C10—H10B···O1ii0.962.573.492 (3)162.
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x−1/2, y+1/2, z.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
O1—H1···O20.821.872.592 (3)146.
C3—H3···O2i0.932.483.356 (3)157.
C10—H10B···O1ii0.962.573.492 (3)162.
Symmetry codes: (i) x, −y+1, z−1/2; (ii) x−1/2, y+1/2, z.
Acknowledgements top

This work was supported by the National Natural Science Foundation (81072577).

references
References top

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