Methyl (R)-2-(2-chloro-phen-yl)-2-(3-nitro-phenyl-sulfon-yloxy)acetate.

The reaction between methyl (R)-2-(2-chloro-phen-yl)-2-hy-droxy-acetate and 3-nitro-benzene-sulfonyl chloride gave the title compound, C(15)H(12)ClNO(7)S, which is a promising inter-mediate for the synthesis of Clopidrogel, an anti-platelet drug used in the prevention of strokes and heart attacks. In the crystal, mol-ecules 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 = 385.77

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.086

S = 1.02

3153 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.21 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: Flack (1983 ▶), 1209 Friedel pairs

Flack parameter: 0.07 (7)

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 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812020016/zl2477sup1.cif

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

Supplementary material file. DOI: 10.1107/S1600536812020016/zl2477Isup3.cml

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

C15H12ClNO7S	F(000) = 792
Mr = 385.77	Dx = 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

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

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(Fo2) + (0.0393P)2 + 0.1718P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
3153 reflections	Δρmax = 0.21 e Å−3
227 parameters	Δρmin = −0.21 e Å−3
0 restraints	Absolute structure: Flack (1983), 1209 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.07 (7)

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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)

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) ; (ii) .