Methyl (R)-2-(2-chloro­phen­yl)-2-(3-nitro­phenyl­sulfon­yloxy)acetate

Li, Y.-H.; Xu, H.-W.; Zhang, L.-X.

doi:10.1107/S1600536812020016

organic compounds

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Volume 68| Part 6| June 2012| Page o1689

doi:10.1107/S1600536812020016

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Methyl (R)-2-(2-chlorophenyl)-2-(3-nitrophenylsulfonyloxy)acetate

Ying-Hua Li,^a Hong-Wu Xu ^a ^* and Liu-Xue Zhang ^a

^aDepartment of Materials and Chemical Engineering, Zhongyuan University of Technology, Zhengzhou, Henan 450007, People's Republic of China
^*Correspondence e-mail: hongwuxu2006@126.com

(Received 28 April 2012; accepted 4 May 2012; online 12 May 2012)

The reaction between methyl (R)-2-(2-chlorophenyl)-2-hydroxyacetate and 3-nitrobenzenesulfonyl chloride gave the title compound, C₁₅H₁₂ClNO₇S, which is a promising intermediate for the synthesis of Clopidrogel, an antiplatelet drug used in the prevention of strokes and heart attacks. In the crystal, molecules are linked through C—H⋯O interactions, and there is also a short Cl⋯O contact present [Cl⋯O = 3.018 (2) Å].

Related literature

For the synthesis of (R)-2-(2-chlorophenyl)-2-hydroxyacetic acid, see: Bousquet & Musolino (2003 ). For related structures, see: Sun et al. (2007 ); Andersen et al. (2007 ). For the synthesis of Clopidrogel from sulfonyloxyacetic esters of (R)-2-(2-chlorophenyl)-2-hydroxyacetic acid, see: Bousquet & Musolino (1999 ); Castaldi et al. (2003 ); Ema et al. (2007 ); Zhu et al. (2010 ). For halogen bonds, see: Bianchi et al. (2004 ); Fourmigue (2009 ); Metrangolo et al. (2005 ).

Experimental

Crystal data

C₁₅H₁₂ClNO₇S
M_r = 385.77
Orthorhombic, P 2₁ 2₁ 2₁
a = 7.5791 (3) Å
b = 11.0242 (5) Å
c = 19.6736 (7) Å
V = 1643.80 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.22 mm

Data collection

Agilent Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (Crysalis PRO; Agilent, 2011 ) T_min = 0.890, T_max = 0.918
5654 measured reflections
3153 independent reflections
2680 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.086
S = 1.02
3153 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ), 1209 Friedel pairs
Flack parameter: 0.07 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H5⋯O4	0.93	2.55	2.920 (4)	104
C14—H5⋯O1ⁱ	0.93	2.60	3.323 (4)	135
C15—H8C⋯O5ⁱⁱ	0.96	2.53	3.419 (4)	155
Symmetry codes: (i) x+1, y, z; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: Crysalis PRO (Agilent, 2011); cell refinement: Crysalis PRO; data reduction: Crysalis PRO; 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812020016/zl2477sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020016/zl2477Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020016/zl2477Isup3.cml

checkCIF report

Comment top

Sulfonyloxyacetic esters of (R)-methyl-2-(2-chlorophenyl)-2-hydroxyacetate are commonly used in the synthesis of Clopidrogel, an antiplatelet drug used in the prevention of strokes and heart attacks (sold in the United States under the brand name of Plavix) (Bousquet & Musolino, 1999; Castaldi et al., 2003; Ema et al., 2007; Zhu et al., 2010). The title compound, a promising intermediate for the synthesis of Clopidrogel, was obtained in two steps from (R)-2-(2-chlorophenyl)-2-hydroxyacetic acid (Bousquet & Musolino, 2003). We report here its crystal structure. In the molecule of the title compound (Fig. 1), the main bond lengths and angles are close to those found in some other derivatives of (R)-methyl-2-(2-chlorophenyl)-2-hydroxyacetate (for example, (R)-methyl-2-(2-chlorophenyl)-2-(benzenesulfonyloxy) acetate and 4aR,11R,11aS)-11-methyl-9- (trifluoromethyl)-1,2,2,3,4,4a,5,6,11,11adecahydro-pyrido[4,3-b] carbazole (R)-2-chloromandelate (Sun et al., 2007; Andersen et al., 2007). The crystal structure of this compound is stabilized by an intermolecular halogen bond (Bianchi et al., 2004; Fourmigue, 2009; Metrangolo et al., 2005) between the Cl atom and one of the O atoms of the SO₂ group of an adjacent molecule, with a C4–Cl1···O4ⁱ separation of 3.018 (2) Å (Fig. 2 and Table 1). Symmetry code (i): x - 1, y, z. The crystal structure is also stabilized by intermolecular C–H···O hydrogen bonding interactions (Table 1).

Related literature top

For the synthesis of (R)-2-(2-chlorophenyl)-2-hydroxyacetic acid, see: Bousquet & Musolino (2003); for related structures, see: Sun et al. (2007); Andersen et al. (2007); for the sythesis of Clopidrogel from sulfonyloxyacetic esters of (R)-2-(2-chlorophenyl)-2-hydroxyacetic acid, see: Bousquet & Musolino (1999); Castaldi et al. (2003); Ema et al. (2007); Zhu et al. (2010). For halogen bonds, see: Bianchi et al. (2004); Fourmigue (2009); Metrangolo et al. (2005).

Experimental top

(R)-2-(2-Chlorophenyl)-2-hydroxyacetic acid and (R)-methyl-2- (2-chlorophenyl)-2-hydroxyacetate were prepared using the established literature procedures (Bousquet et al., 2003, and Sun et al., 2007). A three-necked round-bottomed flask, which was equipped with a magnetic stir bar, was charged with dichloromethane (50 ml), (R)-methyl-2- (2-chlorophenyl)-2-hydroxyacetate (4.5 g), triethylamine (4.3 g), and 4,4-dimethylaminopyridine (275 mg). 3-Nitrobenzenesulfonyl chloride (5.5 g) and dichloromethane (50 ml) were added via syringe. The mixture was stirred at room temperature for 3 h. The reaction mixture was quenched with water, and washed with 1 N HCl (30 ml) twice. The organic layer was dried over anhydrous sodium sulfate and filtered. After concentration under reduced pressure, the residue was purified by silica gel column chromatography with a mixture of petroleum ether and ethyl acetate (4:1 v/v) as eluent to give the title compound (yield, 54%). ¹H NMR (400 MHz, CDCl₃): 8.648 (s, 1H), 8.432 (d, J = 8.0 Hz, 1H), 8.208 (d, J = 8.0 Hz, 1H), 7.704 (t, J = 8.0 Hz, 1H), 7.376 (d, J = 8.0 Hz, 1H), 7.319 - 7.206 (m, 3H), 6.394 (s, 1H), 3.765 (s, 3H) p.p.m.. Well shaped colorless crystals were obtained by slow evaporation of a solution in petroleum ether and ethyl acetate at room temperature for a few days.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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) and PLATON (Spek, 2009).

Figures top

	Fig. 1. A view of the compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the C—Cl···O interaction (dashed lines) in the crystal structure of the title compound. Symmetry code (i): x - 1, y, z.
	Fig. 3. The packing of the compound, viewed down the a axis.

Methyl (R)-2-(2-chlorophenyl)-2-(3-nitrophenylsulfonyloxy)acetate top

Crystal data top

C₁₅H₁₂ClNO₇S	F(000) = 792
M_r = 385.77	D_x = 1.559 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1814 reflections
a = 7.5791 (3) Å	θ = 3.3–26.3°
b = 11.0242 (5) Å	µ = 0.40 mm⁻¹
c = 19.6736 (7) Å	T = 293 K
V = 1643.80 (11) Å³	Prism, colourless
Z = 4	0.30 × 0.25 × 0.22 mm

Data collection top

Agilent Xcalibur Eos Gemini diffractometer	3153 independent reflections
Radiation source: fine-focus sealed tube	2680 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.4°, θ_min = 3.3°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→12
T_min = 0.890, T_max = 0.918	l = −24→15
5654 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.086	w = 1/[σ²(F_o²) + (0.0393P)² + 0.1718P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3153 reflections	Δρ_max = 0.21 e Å⁻³
227 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1209 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.07 (7)

Crystal data top

C₁₅H₁₂ClNO₇S	V = 1643.80 (11) Å³
M_r = 385.77	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.5791 (3) Å	µ = 0.40 mm⁻¹
b = 11.0242 (5) Å	T = 293 K
c = 19.6736 (7) Å	0.30 × 0.25 × 0.22 mm

Data collection top

Agilent Xcalibur Eos Gemini diffractometer	3153 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2680 reflections with I > 2σ(I)
T_min = 0.890, T_max = 0.918	R_int = 0.023
5654 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.086	Δρ_max = 0.21 e Å⁻³
S = 1.02	Δρ_min = −0.21 e Å⁻³
3153 reflections	Absolute structure: Flack (1983), 1209 Friedel pairs
227 parameters	Absolute structure parameter: 0.07 (7)
0 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
S1	0.47477 (9)	0.03812 (6)	0.23919 (4)	0.03772 (18)
Cl1	−0.05655 (10)	0.08212 (8)	0.36889 (4)	0.0513 (2)
N1	0.2766 (4)	0.3236 (3)	0.04654 (14)	0.0554 (7)
O7	0.1312 (4)	0.2781 (3)	0.05356 (13)	0.0763 (8)
O6	0.3113 (4)	0.4007 (2)	0.00436 (14)	0.0820 (8)
O5	0.4263 (3)	−0.06820 (17)	0.20270 (10)	0.0474 (5)
O4	0.6140 (3)	0.0334 (2)	0.28718 (11)	0.0540 (6)
O2	0.1443 (3)	0.36269 (18)	0.33486 (10)	0.0449 (5)
O1	0.0857 (3)	0.2602 (2)	0.23895 (10)	0.0544 (6)
O3	0.2979 (2)	0.07757 (16)	0.27557 (9)	0.0342 (4)
C10	0.3826 (4)	0.1918 (3)	0.13767 (14)	0.0400 (7)
H1A	0.2728	0.1541	0.1383	0.048*
C11	0.4194 (4)	0.2837 (3)	0.09275 (14)	0.0417 (7)
C12	0.5830 (4)	0.3385 (3)	0.08930 (16)	0.0496 (8)
H3	0.6055	0.3984	0.0571	0.060*
C13	0.7118 (4)	0.3032 (3)	0.13422 (17)	0.0504 (8)
H4	0.8222	0.3399	0.1327	0.061*
C14	0.6791 (4)	0.2137 (3)	0.18141 (16)	0.0442 (7)
H5	0.7656	0.1913	0.2125	0.053*
C9	0.5149 (4)	0.1576 (2)	0.18190 (13)	0.0369 (6)
C1	0.1619 (4)	0.2713 (3)	0.29162 (14)	0.0371 (6)
C15	0.0212 (4)	0.4558 (3)	0.31462 (17)	0.0591 (9)
H8A	0.0540	0.4868	0.2708	0.089*
H8B	0.0231	0.5204	0.3473	0.089*
H8C	−0.0954	0.4221	0.3123	0.089*
C2	0.3017 (3)	0.1846 (2)	0.31890 (13)	0.0336 (6)
H9	0.4171	0.2235	0.3133	0.040*
C3	0.2823 (4)	0.1498 (2)	0.39238 (14)	0.0352 (6)
C8	0.4258 (4)	0.1657 (3)	0.43647 (15)	0.0473 (7)
H11	0.5314	0.1963	0.4196	0.057*
C7	0.4125 (5)	0.1367 (3)	0.50432 (17)	0.0584 (9)
H12	0.5084	0.1482	0.5331	0.070*
C6	0.2564 (5)	0.0905 (3)	0.52935 (15)	0.0588 (10)
H13	0.2472	0.0717	0.5753	0.071*
C5	0.1147 (5)	0.0719 (3)	0.48751 (15)	0.0495 (8)
H14	0.0108	0.0391	0.5046	0.059*
C4	0.1279 (4)	0.1026 (3)	0.41929 (13)	0.0378 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0318 (3)	0.0408 (4)	0.0406 (4)	0.0007 (3)	0.0028 (3)	0.0023 (3)
Cl1	0.0389 (4)	0.0714 (5)	0.0437 (4)	−0.0063 (4)	−0.0013 (3)	0.0053 (4)
N1	0.069 (2)	0.0531 (17)	0.0436 (15)	0.0037 (16)	−0.0046 (15)	0.0024 (14)
O7	0.0629 (16)	0.100 (2)	0.0655 (16)	−0.0087 (15)	−0.0233 (14)	0.0133 (16)
O6	0.104 (2)	0.0721 (18)	0.0705 (16)	0.0062 (17)	−0.0065 (17)	0.0295 (16)
O5	0.0533 (13)	0.0350 (11)	0.0539 (12)	0.0010 (9)	0.0129 (11)	−0.0059 (9)
O4	0.0383 (11)	0.0687 (14)	0.0548 (13)	0.0030 (11)	−0.0034 (10)	0.0141 (12)
O2	0.0473 (12)	0.0420 (11)	0.0456 (11)	0.0095 (9)	0.0025 (10)	0.0033 (10)
O1	0.0526 (13)	0.0699 (15)	0.0407 (11)	0.0089 (11)	−0.0095 (11)	0.0048 (11)
O3	0.0314 (9)	0.0376 (10)	0.0338 (9)	−0.0052 (8)	0.0008 (8)	−0.0048 (8)
C10	0.0378 (15)	0.0438 (17)	0.0384 (15)	−0.0057 (13)	−0.0006 (13)	−0.0064 (14)
C11	0.0507 (18)	0.0399 (16)	0.0345 (14)	0.0000 (14)	−0.0008 (14)	−0.0044 (13)
C12	0.064 (2)	0.0359 (16)	0.0491 (18)	−0.0059 (15)	0.0150 (18)	0.0029 (14)
C13	0.0412 (17)	0.0444 (18)	0.066 (2)	−0.0113 (14)	0.0076 (17)	−0.0015 (17)
C14	0.0352 (16)	0.0423 (16)	0.0551 (18)	−0.0029 (13)	0.0016 (15)	−0.0037 (15)
C9	0.0364 (15)	0.0370 (14)	0.0373 (14)	−0.0026 (12)	0.0047 (13)	−0.0016 (12)
C1	0.0303 (15)	0.0449 (16)	0.0361 (14)	−0.0003 (12)	0.0022 (13)	0.0069 (14)
C15	0.056 (2)	0.056 (2)	0.066 (2)	0.0220 (17)	0.0167 (18)	0.0188 (18)
C2	0.0305 (14)	0.0344 (14)	0.0360 (14)	−0.0042 (12)	−0.0024 (13)	−0.0030 (12)
C3	0.0426 (15)	0.0288 (14)	0.0342 (14)	0.0039 (12)	−0.0077 (13)	−0.0058 (12)
C8	0.0567 (19)	0.0361 (16)	0.0493 (17)	−0.0013 (14)	−0.0122 (17)	−0.0049 (14)
C7	0.080 (3)	0.0479 (19)	0.0473 (18)	0.0004 (19)	−0.0303 (19)	−0.0086 (16)
C6	0.094 (3)	0.0486 (19)	0.0340 (16)	0.0087 (19)	−0.0082 (19)	−0.0031 (16)
C5	0.066 (2)	0.0449 (18)	0.0378 (15)	0.0056 (16)	0.0015 (15)	0.0010 (14)
C4	0.0425 (16)	0.0377 (15)	0.0332 (14)	0.0062 (12)	−0.0016 (13)	−0.0024 (13)

Geometric parameters (Å, º) top

S1—O4	1.417 (2)	C13—H4	0.9300
S1—O4	1.417 (2)	C14—C9	1.390 (4)
S1—O5	1.423 (2)	C14—H5	0.9300
S1—O3	1.5809 (18)	C1—C2	1.524 (4)
S1—C9	1.760 (3)	C15—H8A	0.9600
Cl1—C4	1.728 (3)	C15—H8B	0.9600
N1—O6	1.217 (3)	C15—H8C	0.9600
N1—O7	1.218 (4)	C2—C3	1.503 (4)
N1—C11	1.480 (4)	C2—H9	0.9800
O2—C1	1.326 (3)	C3—C4	1.386 (4)
O2—C15	1.443 (3)	C3—C8	1.402 (4)
O1—C1	1.192 (3)	C8—C7	1.376 (4)
O3—C2	1.456 (3)	C8—H11	0.9300
C10—C11	1.373 (4)	C7—C6	1.379 (5)
C10—C9	1.380 (4)	C7—H12	0.9300
C10—H1A	0.9300	C6—C5	1.368 (4)
C11—C12	1.381 (4)	C6—H13	0.9300
C12—C13	1.374 (4)	C5—C4	1.388 (4)
C12—H3	0.9300	C5—H14	0.9300
C13—C14	1.377 (4)

O4—S1—O5	119.91 (14)	O1—C1—C2	125.3 (3)
O4—S1—O5	119.91 (14)	O2—C1—C2	108.7 (2)
O4—S1—O3	109.87 (11)	O2—C15—H8A	109.5
O4—S1—O3	109.87 (11)	O2—C15—H8B	109.5
O5—S1—O3	103.66 (11)	H8A—C15—H8B	109.5
O4—S1—C9	108.98 (13)	O2—C15—H8C	109.5
O4—S1—C9	108.98 (13)	H8A—C15—H8C	109.5
O5—S1—C9	109.75 (12)	H8B—C15—H8C	109.5
O3—S1—C9	103.33 (12)	O3—C2—C3	110.7 (2)
O6—N1—O7	124.1 (3)	O3—C2—C1	106.7 (2)
O6—N1—C11	117.9 (3)	C3—C2—C1	115.5 (2)
O7—N1—C11	118.0 (3)	O3—C2—H9	107.9
C1—O2—C15	115.4 (2)	C3—C2—H9	107.9
C2—O3—S1	118.10 (15)	C1—C2—H9	107.9
C11—C10—C9	117.4 (3)	C4—C3—C8	117.7 (3)
C11—C10—H1A	121.3	C4—C3—C2	123.1 (2)
C9—C10—H1A	121.3	C8—C3—C2	119.2 (3)
C10—C11—C12	122.5 (3)	C7—C8—C3	121.0 (3)
C10—C11—N1	117.7 (3)	C7—C8—H11	119.5
C12—C11—N1	119.8 (3)	C3—C8—H11	119.5
C13—C12—C11	118.8 (3)	C8—C7—C6	119.6 (3)
C13—C12—H3	120.6	C8—C7—H12	120.2
C11—C12—H3	120.6	C6—C7—H12	120.2
C12—C13—C14	120.6 (3)	C5—C6—C7	120.9 (3)
C12—C13—H4	119.7	C5—C6—H13	119.5
C14—C13—H4	119.7	C7—C6—H13	119.5
C13—C14—C9	119.0 (3)	C6—C5—C4	119.3 (3)
C13—C14—H5	120.5	C6—C5—H14	120.4
C9—C14—H5	120.5	C4—C5—H14	120.4
C10—C9—C14	121.6 (3)	C3—C4—C5	121.4 (3)
C10—C9—S1	118.9 (2)	C3—C4—Cl1	120.9 (2)
C14—C9—S1	119.5 (2)	C5—C4—Cl1	117.7 (2)
O1—C1—O2	125.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H5···O4	0.93	2.55	2.920 (4)	104
C14—H5···O1ⁱ	0.93	2.60	3.323 (4)	135
C15—H8C···O5ⁱⁱ	0.96	2.53	3.419 (4)	155
C4—Cl1···O4ⁱⁱⁱ	1.73 (1)	3.02 (1)	4.744 (4)	176 (1)

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂ClNO₇S
M_r	385.77
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	7.5791 (3), 11.0242 (5), 19.6736 (7)
V (Å³)	1643.80 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.30 × 0.25 × 0.22

Data collection
Diffractometer	Agilent Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.890, 0.918
No. of measured, independent and observed [I > 2σ(I)] reflections	5654, 3153, 2680
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.086, 1.02
No. of reflections	3153
No. of parameters	227
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.21
Absolute structure	Flack (1983), 1209 Friedel pairs
Absolute structure parameter	0.07 (7)

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H5···O4	0.93	2.55	2.920 (4)	104.1
C14—H5···O1ⁱ	0.93	2.60	3.323 (4)	135.4
C15—H8C···O5ⁱⁱ	0.96	2.53	3.419 (4)	154.5
C4—Cl1···O4ⁱⁱⁱ	1.728 (3)	3.018 (2)	4.744 (4)	176.27 (12)

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

Acknowledgements

This work was supported by the Program for Science and Technology Innovation Talents at the Universities of Henan Province (grant No. 2011HASTIT022).

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