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

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

doi:10.1107/S1600536811051014

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o4

doi:10.1107/S1600536811051014

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

Le-Xing Xu,^a Xiao-Guang Bai,^a Ju-Xian Wang ^a and Yu-Cheng Wang ^a ^*

^aInstitute of Medicinal Biotechnology, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, People's Republic of China
^*Correspondence e-mail: hongzhaoupr@yahoo.com

(Received 9 November 2011; accepted 28 November 2011; online 3 December 2011)

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).

Related literature

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

Crystal data

C₁₀H₈Cl₂O₃
M_r = 247.06
Monoclinic, C c
a = 15.889 (3) Å
b = 3.8242 (8) Å
c = 18.204 (4) Å
β = 108.18 (3)°
V = 1050.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.60 mm⁻¹
T = 294 K
0.25 × 0.20 × 0.15 mm

Data collection

Rigaku SCXmini diffractometer
5011 measured reflections
2371 independent reflections
2170 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.086
S = 1.07
2371 reflections
139 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ), 1177 Friedel pairs
Flack parameter: 0.07 (6)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2	0.82	1.87	2.592 (3)	146
C3—H3⋯O2ⁱ	0.93	2.48	3.356 (3)	157
C10—H10B⋯O1ⁱⁱ	0.96	2.57	3.492 (3)	162
Symmetry codes: (i) $[x, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: CrystalClear (Rigaku, 2005 ); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811051014/lr2037sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811051014/lr2037Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811051014/lr2037Isup3.cml

checkCIF report

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.

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

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
	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

C₁₀H₈Cl₂O₃	F(000) = 504
M_r = 247.06	D_x = 1.562 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 5046 reflections
a = 15.889 (3) Å	θ = 3.3–27.0°
b = 3.8242 (8) Å	µ = 0.60 mm⁻¹
c = 18.204 (4) Å	T = 294 K
β = 108.18 (3)°	Prism, colorless
V = 1050.9 (4) Å³	0.25 × 0.20 × 0.15 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	2170 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 27.5°, θ_min = 4.1°
Detector resolution: 13.6612 pixels mm^-1	h = −20→20
CCD_Profile_fitting scans	k = −4→4
5011 measured reflections	l = −23→23
2371 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.034	w = 1/[σ²(F_o²) + (0.0413P)² + 0.0839P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.086	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.17 e Å⁻³
2371 reflections	Δρ_min = −0.18 e Å⁻³
139 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0193 (14)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1177 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.07 (6)

Crystal data top

C₁₀H₈Cl₂O₃	V = 1050.9 (4) Å³
M_r = 247.06	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 15.889 (3) Å	µ = 0.60 mm⁻¹
b = 3.8242 (8) Å	T = 294 K
c = 18.204 (4) Å	0.25 × 0.20 × 0.15 mm
β = 108.18 (3)°

Data collection top

Rigaku SCXmini diffractometer	2170 reflections with I > 2σ(I)
5011 measured reflections	R_int = 0.030
2371 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.086	Δρ_max = 0.17 e Å⁻³
S = 1.07	Δρ_min = −0.18 e Å⁻³
2371 reflections	Absolute structure: Flack (1983), 1177 Friedel pairs
139 parameters	Absolute structure 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

	x	y	z	U_iso*/U_eq
C1	0.58573 (13)	0.7958 (6)	0.44452 (12)	0.0381 (5)
C2	0.53832 (13)	0.7161 (6)	0.36792 (12)	0.0392 (5)
C3	0.57482 (16)	0.7526 (7)	0.30884 (13)	0.0439 (5)
H3	0.5423	0.6944	0.2583	0.053*
C4	0.65998 (16)	0.8762 (6)	0.32574 (14)	0.0478 (5)
C5	0.70941 (16)	0.9602 (7)	0.40023 (15)	0.0520 (6)
H5	0.7669	1.0447	0.4109	0.062*
C6	0.67267 (16)	0.9175 (7)	0.45842 (14)	0.0495 (6)
H6	0.7065	0.9709	0.5088	0.059*
C7	0.55234 (15)	0.7569 (6)	0.51099 (12)	0.0424 (5)
C8	0.47153 (15)	0.8564 (6)	0.51265 (13)	0.0424 (5)
H8	0.4315	0.9548	0.4689	0.051*
C9	0.44659 (15)	0.8113 (7)	0.58190 (13)	0.0441 (5)
C10	0.3367 (2)	0.8937 (8)	0.64204 (16)	0.0612 (7)
H10A	0.3348	0.6501	0.6542	0.092*
H10B	0.2787	0.9934	0.6319	0.092*
H10C	0.3776	1.0126	0.6849	0.092*
Cl1	0.43104 (3)	0.55059 (16)	0.34217 (3)	0.05160 (19)
Cl2	0.70467 (4)	0.9249 (2)	0.25046 (4)	0.0757 (3)
O1	0.61264 (12)	0.6173 (6)	0.57216 (10)	0.0629 (5)
H1	0.5931	0.6120	0.6088	0.094*
O2	0.49301 (12)	0.6776 (6)	0.64092 (9)	0.0620 (5)
O3	0.36513 (11)	0.9310 (5)	0.57450 (9)	0.0521 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0333 (10)	0.0443 (11)	0.0353 (10)	−0.0018 (9)	0.0086 (8)	−0.0022 (8)
C2	0.0305 (9)	0.0449 (12)	0.0401 (11)	−0.0029 (8)	0.0081 (8)	−0.0011 (9)
C3	0.0384 (10)	0.0573 (13)	0.0350 (12)	−0.0029 (10)	0.0103 (10)	−0.0052 (10)
C4	0.0450 (12)	0.0598 (15)	0.0441 (12)	0.0013 (11)	0.0218 (10)	0.0021 (11)
C5	0.0355 (11)	0.0657 (15)	0.0541 (14)	−0.0083 (10)	0.0130 (11)	−0.0040 (12)
C6	0.0368 (12)	0.0687 (15)	0.0386 (12)	−0.0056 (11)	0.0056 (10)	−0.0073 (10)
C7	0.0412 (11)	0.0494 (12)	0.0329 (11)	−0.0003 (9)	0.0062 (9)	−0.0009 (9)
C8	0.0390 (11)	0.0525 (13)	0.0349 (11)	0.0029 (9)	0.0104 (9)	0.0063 (10)
C9	0.0423 (12)	0.0534 (13)	0.0366 (11)	0.0007 (10)	0.0124 (10)	0.0003 (10)
C10	0.0577 (15)	0.083 (2)	0.0505 (15)	0.0069 (14)	0.0281 (13)	0.0036 (13)
Cl1	0.0372 (3)	0.0734 (4)	0.0422 (3)	−0.0139 (3)	0.0093 (2)	−0.0054 (3)
Cl2	0.0592 (4)	0.1199 (7)	0.0596 (4)	−0.0099 (5)	0.0351 (4)	0.0000 (5)
O1	0.0466 (9)	0.1045 (15)	0.0347 (9)	0.0182 (10)	0.0085 (7)	0.0137 (9)
O2	0.0507 (10)	0.0981 (14)	0.0363 (9)	0.0163 (10)	0.0124 (8)	0.0170 (9)
O3	0.0434 (8)	0.0738 (12)	0.0412 (9)	0.0096 (8)	0.0164 (7)	0.0078 (8)

Geometric parameters (Å, º) top

C1—C2	1.396 (3)	C7—O1	1.333 (3)
C1—C6	1.404 (3)	C7—C8	1.349 (3)
C1—C7	1.472 (3)	C8—C9	1.445 (3)
C2—C3	1.379 (3)	C8—H8	0.9300
C2—Cl1	1.740 (2)	C9—O2	1.210 (3)
C3—C4	1.375 (3)	C9—O3	1.340 (3)
C3—H3	0.9300	C10—O3	1.443 (3)
C4—C5	1.376 (4)	C10—H10A	0.9600
C4—Cl2	1.739 (2)	C10—H10B	0.9600
C5—C6	1.370 (3)	C10—H10C	0.9600
C5—H5	0.9300	O1—H1	0.8200
C6—H6	0.9300

C2—C1—C6	116.5 (2)	O1—C7—C8	122.4 (2)
C2—C1—C7	125.31 (18)	O1—C7—C1	112.18 (19)
C6—C1—C7	118.17 (19)	C8—C7—C1	125.4 (2)
C3—C2—C1	121.98 (19)	C7—C8—C9	120.5 (2)
C3—C2—Cl1	116.21 (16)	C7—C8—H8	119.7
C1—C2—Cl1	121.77 (16)	C9—C8—H8	119.7
C4—C3—C2	119.0 (2)	O2—C9—O3	122.4 (2)
C4—C3—H3	120.5	O2—C9—C8	124.6 (2)
C2—C3—H3	120.5	O3—C9—C8	113.00 (19)
C3—C4—C5	121.3 (2)	O3—C10—H10A	109.5
C3—C4—Cl2	118.42 (19)	O3—C10—H10B	109.5
C5—C4—Cl2	120.24 (19)	H10A—C10—H10B	109.5
C6—C5—C4	119.0 (2)	O3—C10—H10C	109.5
C6—C5—H5	120.5	H10A—C10—H10C	109.5
C4—C5—H5	120.5	H10B—C10—H10C	109.5
C5—C6—C1	122.2 (2)	C7—O1—H1	109.5
C5—C6—H6	118.9	C9—O3—C10	115.47 (19)
C1—C6—H6	118.9

C6—C1—C2—C3	0.4 (4)	C7—C1—C6—C5	179.7 (2)
C7—C1—C2—C3	−178.6 (2)	C2—C1—C7—O1	136.9 (2)
C6—C1—C2—Cl1	178.08 (18)	C6—C1—C7—O1	−42.0 (3)
C7—C1—C2—Cl1	−0.9 (3)	C2—C1—C7—C8	−44.8 (3)
C1—C2—C3—C4	−1.0 (4)	C6—C1—C7—C8	136.3 (3)
Cl1—C2—C3—C4	−178.9 (2)	O1—C7—C8—C9	−0.6 (4)
C2—C3—C4—C5	0.7 (4)	C1—C7—C8—C9	−178.8 (2)
C2—C3—C4—Cl2	−179.34 (19)	C7—C8—C9—O2	−2.1 (4)
C3—C4—C5—C6	0.3 (4)	C7—C8—C9—O3	178.5 (2)
Cl2—C4—C5—C6	−179.7 (2)	O2—C9—O3—C10	0.7 (4)
C4—C5—C6—C1	−1.0 (4)	C8—C9—O3—C10	−179.9 (2)
C2—C1—C6—C5	0.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.87	2.592 (3)	146
C3—H3···O2ⁱ	0.93	2.48	3.356 (3)	157
C10—H10B···O1ⁱⁱ	0.96	2.57	3.492 (3)	162

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

Experimental details

Crystal data
Chemical formula	C₁₀H₈Cl₂O₃
M_r	247.06
Crystal system, space group	Monoclinic, Cc
Temperature (K)	294
a, b, c (Å)	15.889 (3), 3.8242 (8), 18.204 (4)
β (°)	108.18 (3)
V (Å³)	1050.9 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.60
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5011, 2371, 2170
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.086, 1.07
No. of reflections	2371
No. of parameters	139
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.18
Absolute structure	Flack (1983), 1177 Friedel pairs
Absolute structure parameter	0.07 (6)

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.87	2.592 (3)	145.6
C3—H3···O2ⁱ	0.93	2.48	3.356 (3)	156.5
C10—H10B···O1ⁱⁱ	0.96	2.57	3.492 (3)	162.4

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

Acknowledgements

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

References

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