Dimethyl 2-chloro-3-tosyl­maleate

The title compound, C₁₃H₁₃ClO₆S, contains two methoxy­carbonyl groups in a cis arrangement, with a dihedral angle of 79.9 (1)° between the least-squares planes defined by the two methoxy­carbonyl fragments. Weak van der Waals inter­actions between the mol­ecules are effective in the mol­ecular packing. This is the first X-ray structure reported for a tosyl­maleate derivative which can be used as a pharmaceutical primary material.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.045
• wR factor = 0.127
• Data-to-parameter ratio = 17.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O1      ..       3.09 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Vinylsulfonyl groups are valuable building blocks which can be used in fiber-reactive azo dyes, and also in plastic films and photographic materials (Zhu et al., 1989). The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. The two methoxycarbonyl groups are in cis configuration, shown by the torsion angle C5—C1—C2—C3 close to 0°. The interplanar angle between the least-squares planes defined by O6/C3/C2/O5/C4 and O4/C5/C1/O3/C6 is 79.9 (1)°. The four atoms connected to ethylene functionality (C1═C2) only slightly deviate from planarity. Relatively weak intermolecular van der Waals interactions are present between neighboring molecules, stabilizing the crystal structure.

Related literature

For applications of vinylsulfonyl containing compounds, see: Zhu et al. (1989).

S2. Experimental

To a solution of dimethyl acetylenedicarboxylate (DMAD, 566 mg, 4.0 mmol) and p-toluenesulfonyl chloride (4.0 mmol) in dry THF (15 ml) under a nitrogen atmosphere, pyridine (48 mg, 0.6 mmol) was added and the reaction mixture was stirred for 16 h at room temperature. The solvent was evaporated and the residue was chromatographed on a silicagel column, using hexane-ethylacetate (90/10) as eluent, giving the pure product.

S3. Refinement

All H atoms were positioned geometrically and constrained to ride on their parent atoms, with U_iso(H) = 1.2 or 1.5 times U_eq(carrier C) for aromatic and methyl group, respectively. C—H bond lengths were set to 0.93 (aromatic CH) and 0.96 Å (methyl CH₃), and methyl groups were allowed to rotate about their C—C σ bonds.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: PLATON (Spek, 2003).

Figures

Fig. 1. Molecular structure of (I), with 50% probability displacement ellipsoids. H atoms are shown as circles of arbitrary radii.

Dimethyl 2-chloro-3-tosylmaleate

Crystal data

C13H13ClO6S	F(000) = 688
Mr = 332.74	Dx = 1.460 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9792 reflections
a = 12.4167 (14) Å	θ = 3.8–32.1°
b = 12.9964 (13) Å	µ = 0.41 mm^−1
c = 9.5511 (10) Å	T = 290 K
β = 100.879 (10)°	Needle, colourless
V = 1513.6 (3) Å^3	0.5 × 0.2 × 0.1 mm
Z = 4

Data collection

Oxford Diffraction X-calibur2 with a Sapphire-3 CCD detector diffractometer	3298 independent reflections
Radiation source: fine-focus sealed tube	2475 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
Detector resolution: 12 pixels mm^-1	θmax = 27.0°, θmin = 3.8°
ω scans at different φ	h = −15→11
Absorption correction: numerical (X-RED; Stoe & Cie, 1997)	k = −16→16
Tmin = 0.815, Tmax = 0.930	l = −12→12
9792 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.127	w = 1/[σ^2(Fo^2) + (0.0868P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
3298 reflections	Δρmax = 0.45 e Å^−3
194 parameters	Δρmin = −0.30 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.040 (4)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.29026 (4)	0.12068 (4)	0.04566 (5)	0.03976 (17)
Cl1	0.14986 (4)	0.12677 (4)	0.30129 (5)	0.04899 (19)
O1	0.23422 (11)	0.21700 (10)	0.04155 (14)	0.0519 (4)
O2	0.32811 (12)	0.08590 (13)	−0.07918 (14)	0.0561 (4)
O3	0.14474 (11)	−0.06627 (11)	−0.13420 (14)	0.0503 (4)
O4	0.26860 (14)	−0.14406 (13)	0.03464 (18)	0.0694 (5)
O5	0.03110 (11)	−0.05397 (11)	0.33034 (14)	0.0511 (4)
O6	0.03986 (14)	−0.12829 (11)	0.12083 (17)	0.0615 (4)
C1	0.20074 (14)	0.01944 (13)	0.08335 (18)	0.0362 (4)
C2	0.14118 (14)	0.02430 (13)	0.18619 (18)	0.0364 (4)
C3	0.06504 (14)	−0.06168 (14)	0.2081 (2)	0.0414 (4)
C4	−0.0495 (2)	−0.1296 (2)	0.3566 (3)	0.0689 (7)
H4A	−0.1066	−0.1351	0.2738	0.103*
H4B	−0.0805	−0.1082	0.4366	0.103*
H4C	−0.0145	−0.1952	0.3766	0.103*
C5	0.20747 (15)	−0.07510 (15)	−0.0063 (2)	0.0433 (4)
C6	0.1592 (2)	−0.1451 (2)	−0.2352 (3)	0.0730 (7)
H6A	0.2359	−0.1536	−0.2356	0.109*
H6B	0.1217	−0.1255	−0.3286	0.109*
H6C	0.1295	−0.2088	−0.2085	0.109*
C7	0.40081 (14)	0.11797 (14)	0.19050 (19)	0.0388 (4)
C8	0.47378 (16)	0.03585 (16)	0.2040 (2)	0.0505 (5)
H8	0.4648	−0.0168	0.1368	0.061*
C9	0.56025 (17)	0.03382 (18)	0.3196 (3)	0.0576 (6)
H9	0.6094	−0.0209	0.3293	0.069*
C10	0.57497 (16)	0.11112 (17)	0.4204 (2)	0.0513 (5)
C11	0.50243 (18)	0.19318 (18)	0.4025 (2)	0.0567 (5)
H11	0.5128	0.2467	0.4683	0.068*
C12	0.41541 (16)	0.19742 (16)	0.2894 (2)	0.0492 (5)
H12	0.3671	0.2528	0.2794	0.059*
C13	0.6695 (2)	0.1068 (2)	0.5454 (3)	0.0758 (8)
H13A	0.6709	0.0407	0.5905	0.114*
H13B	0.6607	0.1595	0.6127	0.114*
H13C	0.7371	0.1175	0.5125	0.114*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0468 (3)	0.0380 (3)	0.0358 (3)	−0.00102 (18)	0.01118 (19)	0.00405 (17)
Cl1	0.0638 (3)	0.0390 (3)	0.0490 (3)	−0.0072 (2)	0.0231 (2)	−0.01039 (19)
O1	0.0611 (8)	0.0384 (8)	0.0553 (8)	0.0041 (6)	0.0086 (7)	0.0135 (6)
O2	0.0679 (9)	0.0641 (10)	0.0404 (7)	−0.0087 (7)	0.0211 (7)	−0.0005 (7)
O3	0.0579 (8)	0.0505 (9)	0.0408 (7)	0.0002 (6)	0.0051 (6)	−0.0117 (6)
O4	0.0798 (11)	0.0528 (10)	0.0716 (11)	0.0271 (8)	0.0036 (8)	−0.0075 (8)
O5	0.0571 (8)	0.0542 (9)	0.0442 (8)	−0.0168 (6)	0.0148 (6)	−0.0004 (6)
O6	0.0792 (11)	0.0456 (9)	0.0629 (10)	−0.0202 (7)	0.0220 (8)	−0.0142 (7)
C1	0.0384 (9)	0.0351 (9)	0.0338 (9)	0.0020 (7)	0.0032 (7)	0.0015 (7)
C2	0.0391 (9)	0.0331 (9)	0.0355 (9)	0.0006 (7)	0.0036 (7)	−0.0006 (7)
C3	0.0447 (10)	0.0365 (10)	0.0425 (10)	−0.0002 (8)	0.0074 (8)	0.0030 (8)
C4	0.0793 (16)	0.0702 (17)	0.0635 (15)	−0.0296 (12)	0.0298 (12)	0.0013 (12)
C5	0.0459 (10)	0.0396 (11)	0.0451 (10)	0.0014 (8)	0.0101 (8)	−0.0040 (8)
C6	0.0771 (16)	0.0788 (18)	0.0636 (15)	−0.0067 (13)	0.0150 (12)	−0.0344 (13)
C7	0.0385 (9)	0.0402 (10)	0.0391 (9)	−0.0024 (7)	0.0112 (7)	0.0013 (7)
C8	0.0486 (11)	0.0470 (12)	0.0563 (12)	0.0059 (9)	0.0106 (9)	−0.0075 (9)
C9	0.0477 (11)	0.0534 (13)	0.0699 (14)	0.0085 (9)	0.0067 (10)	0.0039 (11)
C10	0.0436 (10)	0.0574 (13)	0.0519 (12)	−0.0085 (9)	0.0062 (9)	0.0077 (10)
C11	0.0583 (12)	0.0552 (13)	0.0552 (12)	−0.0025 (10)	0.0067 (10)	−0.0160 (10)
C12	0.0500 (11)	0.0412 (11)	0.0564 (12)	0.0035 (8)	0.0103 (9)	−0.0069 (9)
C13	0.0638 (15)	0.086 (2)	0.0697 (16)	−0.0091 (13)	−0.0085 (12)	0.0109 (14)

Geometric parameters (Å, º)

S1—O1	1.4291 (14)	C6—H6A	0.9600
S1—O2	1.4348 (15)	C6—H6B	0.9600
S1—C7	1.7557 (19)	C6—H6C	0.9600
S1—C1	1.8020 (18)	C7—C12	1.388 (3)
Cl1—C2	1.7172 (18)	C7—C8	1.390 (3)
O3—C5	1.324 (2)	C8—C9	1.387 (3)
O3—C6	1.442 (3)	C8—H8	0.9300
O4—C5	1.192 (2)	C9—C10	1.380 (3)
O5—C3	1.318 (2)	C9—H9	0.9300
O5—C4	1.457 (2)	C10—C11	1.385 (3)
O6—C3	1.201 (2)	C10—C13	1.509 (3)
C1—C2	1.338 (2)	C11—C12	1.377 (3)
C1—C5	1.509 (3)	C11—H11	0.9300
C2—C3	1.504 (2)	C12—H12	0.9300
C4—H4A	0.9600	C13—H13A	0.9600
C4—H4B	0.9600	C13—H13B	0.9600
C4—H4C	0.9600	C13—H13C	0.9600
O1—S1—O2	119.16 (9)	H6A—C6—H6B	109.5
O1—S1—C7	110.09 (9)	O3—C6—H6C	109.5
O2—S1—C7	108.57 (9)	H6A—C6—H6C	109.5
O1—S1—C1	109.24 (8)	H6B—C6—H6C	109.5
O2—S1—C1	104.31 (9)	C12—C7—C8	120.58 (18)
C7—S1—C1	104.36 (8)	C12—C7—S1	120.23 (15)
C5—O3—C6	115.46 (18)	C8—C7—S1	119.19 (15)
C3—O5—C4	116.47 (17)	C9—C8—C7	118.79 (19)
C2—C1—C5	123.54 (16)	C9—C8—H8	120.6
C2—C1—S1	124.02 (14)	C7—C8—H8	120.6
C5—C1—S1	112.27 (13)	C10—C9—C8	121.5 (2)
C1—C2—C3	121.07 (16)	C10—C9—H9	119.3
C1—C2—Cl1	122.01 (14)	C8—C9—H9	119.3
C3—C2—Cl1	116.91 (13)	C9—C10—C11	118.47 (19)
O6—C3—O5	125.76 (17)	C9—C10—C13	120.4 (2)
O6—C3—C2	121.84 (17)	C11—C10—C13	121.1 (2)
O5—C3—C2	112.40 (16)	C12—C11—C10	121.6 (2)
O5—C4—H4A	109.5	C12—C11—H11	119.2
O5—C4—H4B	109.5	C10—C11—H11	119.2
H4A—C4—H4B	109.5	C11—C12—C7	119.09 (19)
O5—C4—H4C	109.5	C11—C12—H12	120.5
H4A—C4—H4C	109.5	C7—C12—H12	120.5
H4B—C4—H4C	109.5	C10—C13—H13A	109.5
O4—C5—O3	126.52 (19)	C10—C13—H13B	109.5
O4—C5—C1	121.76 (18)	H13A—C13—H13B	109.5
O3—C5—C1	111.53 (16)	C10—C13—H13C	109.5
O3—C6—H6A	109.5	H13A—C13—H13C	109.5
O3—C6—H6B	109.5	H13B—C13—H13C	109.5
O1—S1—C1—C2	−46.44 (17)	S1—C1—C5—O4	92.7 (2)
O2—S1—C1—C2	−174.88 (15)	C2—C1—C5—O3	101.9 (2)
C7—S1—C1—C2	71.26 (16)	S1—C1—C5—O3	−82.72 (16)
O1—S1—C1—C5	138.23 (12)	O1—S1—C7—C12	6.95 (18)
O2—S1—C1—C5	9.79 (15)	O2—S1—C7—C12	139.03 (16)
C7—S1—C1—C5	−104.07 (13)	C1—S1—C7—C12	−110.17 (16)
C5—C1—C2—C3	−7.4 (3)	O1—S1—C7—C8	−172.52 (15)
S1—C1—C2—C3	177.75 (12)	O2—S1—C7—C8	−40.44 (18)
C5—C1—C2—Cl1	171.16 (14)	C1—S1—C7—C8	70.36 (17)
S1—C1—C2—Cl1	−3.7 (2)	C12—C7—C8—C9	1.2 (3)
C4—O5—C3—O6	−4.2 (3)	S1—C7—C8—C9	−179.35 (16)
C4—O5—C3—C2	175.59 (17)	C7—C8—C9—C10	0.0 (3)
C1—C2—C3—O6	−13.4 (3)	C8—C9—C10—C11	−1.5 (3)
Cl1—C2—C3—O6	167.92 (16)	C8—C9—C10—C13	179.8 (2)
C1—C2—C3—O5	166.77 (16)	C9—C10—C11—C12	1.8 (3)
Cl1—C2—C3—O5	−11.9 (2)	C13—C10—C11—C12	−179.5 (2)
C6—O3—C5—O4	−4.8 (3)	C10—C11—C12—C7	−0.6 (3)
C6—O3—C5—C1	170.36 (18)	C8—C7—C12—C11	−0.9 (3)
C2—C1—C5—O4	−82.7 (3)	S1—C7—C12—C11	179.65 (16)