7-Benzene­sulfonamido-3-ethenyl-8-oxo-5-thia-1-aza­bicyclo­[4.2.0]oct-2-ene-2-carboxylic acid methanol solvate

Mariam, I.; Akkurt, M.; Sharif, S.; Haider, S.K.; Khan*, I.U.

doi:10.1107/S1600536809024726

7-Benzenesulfonamido-3-ethenyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid methanol solvate

I. Mariam, M. Akkurt, S. Sharif, S. K. Haider and I. U. Khan

In the title compound, C₁₅H₁₄N₂O₅S₂·CH₄O, the six-membered ring fused to the β-lactam unit adopts a twisted conformation. In the crystal structure, the component molecules are linked into a three-dimensional framework through intermolecular N—H

S, N—H

O and O—H

O hydrogen bonds and C—H

O contacts.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809024726/hb5002sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809024726/hb5002Isup2.hkl Contains datablock I

CCDC reference: 744278

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.008 Å
R factor = 0.051
wR factor = 0.120
Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.124
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.92 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C3
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.50
           From the CIF: _reflns_number_total               3862
           Count of symmetry unique reflns         2364
           Completeness (_total/calc)            163.37%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1498
           Fraction of Friedel pairs measured     0.634
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_4_G The Model has Chirality at C7      (Verify) ....          R
PLAT791_ALERT_4_G The Model has Chirality at C9      (Verify) ....          R

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

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

Comment top

(6R,7R)-7-Amino-3-ethenyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2- carboxylic (7-AVCA) is an important intermediate for the synthesis of semi synthetic cephalosporins such as cefixime and cefdinir etc. These antibiotics are synthesized by the reaction of side chains such as amino thiazole thioesters with 7-AVCA (Yamanaka et al. 1985).

A view of compound (I) is shown in Fig. 1: its bond lengths and bond angles are within normal ranges (Allen et al., 1987). In the main molecule of (I), the β-lactam unit (N2/C7—C9) and the six-membered ring fused to the β-lactam unit, (N2/S2/C9—C12) are puckered with the puckering parameters (Cremer & Pople, 1975): Q(2) = -0.102 (5) Å, and Q_T = 0.643 (4) Å, θ = 123.7 (4) °, ϕ = 197.2 (5) °, respectively.

In the crystal packing, intermolecular N—H···O, C—H···O contacts and O—H···O hydrogen bonds stabilize crystal structure (Table 1, Fig. 2).

Related literature top

For background to the use of the title compound in organic synthesis, see: Yamanaka et al. (1985). For ring puckering analysis, see: Cremer & Pople (1975). For reference structural data, see: Allen et al. (1987).

Experimental top

7-AVCA (1 g, 4.4 mmol) was dissolved in distilled water (15 ml) in a round bottom flask (50 ml). 3M Na₂CO₃ solution was used to maintain the solution at pH at 8–9, then benzene sulfonyl chloride (1.1 g, 4.4 mmol) was added to the solution and stirred at room temperature until all the benzene sulfonyl chloride was consumed. When reaction competed, the pH was adjusted 1–2, using 3 N HCl. The precipitate obtained was filtered, washed with distilled water, dried and recrystalized in methanol and ethyl acetate, from which light yellow prisms of (I) appeared after three days.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of the title molecule with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
	Fig. 2. The packing and hydrogen bonding of (I) viewed down b axis. Hydrogen atoms not involved in the showed interactions have been omitted for clarity.

7-Benzenesulfonamido-3-ethenyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene- 2-carboxylic acid methanol solvate top

Crystal data top

C₁₅H₁₄N₂O₅S₂·CH₄O	F(000) = 416
M_r = 398.46	D_x = 1.410 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1813 reflections
a = 12.0000 (2) Å	θ = 2.8–21.7°
b = 6.0964 (8) Å	µ = 0.32 mm⁻¹
c = 13.602 (2) Å	T = 296 K
β = 109.412 (7)°	Prism, light yellow
V = 938.51 (19) Å³	0.31 × 0.28 × 0.11 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	2296 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.125
Graphite monochromator	θ_max = 27.5°, θ_min = 2.8°
ϕ and ω scans	h = −15→15
9995 measured reflections	k = −7→7
3862 independent reflections	l = −17→17

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)] = 0.051	H-atom parameters constrained
wR(F²) = 0.120	w = 1/[σ²(F_o²)], where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max < 0.001
3862 reflections	Δρ_max = 0.30 e Å⁻³
238 parameters	Δρ_min = −0.25 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1498 Freidel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (10)

Crystal data top

C₁₅H₁₄N₂O₅S₂·CH₄O	V = 938.51 (19) Å³
M_r = 398.46	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 12.0000 (2) Å	µ = 0.32 mm⁻¹
b = 6.0964 (8) Å	T = 296 K
c = 13.602 (2) Å	0.31 × 0.28 × 0.11 mm
β = 109.412 (7)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	2296 reflections with I > 2σ(I)
9995 measured reflections	R_int = 0.125
3862 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.120	Δρ_max = 0.30 e Å⁻³
S = 0.96	Δρ_min = −0.25 e Å⁻³
3862 reflections	Absolute structure: Flack (1983), 1498 Freidel pairs
238 parameters	Absolute structure parameter: 0.01 (10)
1 restraint

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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	0.24181 (10)	0.36361 (18)	0.94436 (9)	0.0411 (3)
S2	0.50199 (10)	0.6029 (2)	0.77686 (11)	0.0521 (4)
O1	0.2562 (3)	0.1318 (5)	0.9415 (3)	0.0542 (11)
O2	0.2889 (3)	0.4810 (6)	1.0402 (2)	0.0517 (11)
O3	0.1400 (3)	0.8330 (5)	0.7110 (3)	0.0549 (11)
O4	0.2503 (3)	1.1724 (5)	0.5108 (2)	0.0525 (13)
O5	0.2210 (3)	1.2961 (5)	0.6536 (3)	0.0515 (11)
N1	0.3034 (3)	0.4643 (6)	0.8640 (3)	0.0429 (12)
N2	0.3414 (3)	0.9197 (6)	0.7515 (3)	0.0395 (11)
C1	0.0903 (4)	0.4207 (8)	0.8928 (4)	0.0452 (16)
C2	0.0153 (5)	0.2642 (10)	0.8338 (5)	0.072 (2)
C3	−0.1051 (6)	0.3020 (13)	0.7971 (6)	0.106 (3)
C4	−0.1480 (5)	0.4972 (15)	0.8162 (6)	0.106 (4)
C5	−0.0732 (6)	0.6566 (11)	0.8740 (6)	0.083 (3)
C6	0.0463 (5)	0.6175 (9)	0.9130 (4)	0.0605 (19)
C7	0.3184 (4)	0.7005 (7)	0.8608 (4)	0.0382 (14)
C8	0.2425 (4)	0.8224 (7)	0.7622 (4)	0.0395 (16)
C9	0.4254 (4)	0.7890 (7)	0.8338 (3)	0.0414 (14)
C10	0.3684 (4)	1.0245 (7)	0.6711 (3)	0.0363 (12)
C11	0.4728 (4)	0.9955 (8)	0.6583 (4)	0.0430 (16)
C12	0.5600 (4)	0.8213 (8)	0.7183 (4)	0.0477 (16)
C13	0.5131 (4)	1.1393 (8)	0.5911 (4)	0.0505 (17)
C14	0.6165 (5)	1.1290 (11)	0.5780 (4)	0.066 (2)
C15	0.2738 (4)	1.1796 (7)	0.6118 (4)	0.0396 (16)
O6	−0.0926 (3)	0.9464 (6)	0.5948 (3)	0.0612 (13)
C16	−0.0774 (5)	1.1397 (11)	0.5436 (5)	0.087 (3)
H1	0.32650	0.37930	0.82420	0.0510*
H2	0.04550	0.13290	0.81850	0.0860*
H3	−0.15650	0.19400	0.75960	0.1280*
H4	−0.22890	0.52390	0.79000	0.1270*
H4A	0.19880	1.26240	0.48270	0.0790*
H5	−0.10350	0.79010	0.88660	0.1000*
H6	0.09720	0.72360	0.95290	0.0730*
H7	0.31290	0.77040	0.92390	0.0450*
H9	0.47870	0.87900	0.88940	0.0490*
H12A	0.62240	0.89400	0.77300	0.0570*
H12B	0.59600	0.75590	0.67110	0.0570*
H13	0.46110	1.24730	0.55440	0.0600*
H14A	0.67120	1.02350	0.61320	0.0790*
H14B	0.63520	1.22730	0.53350	0.0790*
H6A	−0.02910	0.90940	0.63720	0.0920*
H16A	−0.14900	1.22400	0.52400	0.1300*
H16B	−0.05870	1.10180	0.48230	0.1300*
H16C	−0.01400	1.22470	0.58960	0.1300*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0419 (6)	0.0356 (6)	0.0425 (6)	0.0064 (5)	0.0098 (5)	0.0033 (6)
S2	0.0394 (6)	0.0459 (7)	0.0678 (9)	0.0128 (6)	0.0135 (6)	0.0032 (7)
O1	0.061 (2)	0.0331 (18)	0.068 (2)	0.0099 (15)	0.0208 (18)	0.0053 (17)
O2	0.057 (2)	0.056 (2)	0.0372 (19)	0.0017 (16)	0.0091 (16)	0.0000 (16)
O3	0.0350 (16)	0.061 (2)	0.061 (2)	0.0070 (16)	0.0055 (16)	0.0100 (19)
O4	0.0470 (19)	0.068 (3)	0.0376 (19)	0.0172 (15)	0.0074 (16)	0.0061 (17)
O5	0.0476 (18)	0.056 (2)	0.046 (2)	0.0181 (15)	0.0092 (16)	−0.0005 (16)
N1	0.051 (2)	0.035 (2)	0.047 (2)	0.0085 (17)	0.022 (2)	−0.0006 (18)
N2	0.0324 (18)	0.040 (2)	0.042 (2)	0.0113 (15)	0.0070 (16)	0.0087 (17)
C1	0.040 (2)	0.048 (3)	0.046 (3)	0.006 (2)	0.012 (2)	0.002 (2)
C2	0.055 (3)	0.066 (4)	0.083 (4)	0.011 (3)	0.006 (3)	−0.023 (3)
C3	0.053 (4)	0.117 (6)	0.124 (7)	0.005 (4)	−0.004 (4)	−0.036 (5)
C4	0.041 (4)	0.141 (7)	0.115 (7)	0.032 (4)	−0.001 (4)	−0.008 (6)
C5	0.074 (4)	0.088 (5)	0.091 (5)	0.035 (4)	0.032 (4)	0.003 (4)
C6	0.064 (3)	0.053 (3)	0.063 (4)	0.019 (3)	0.019 (3)	−0.004 (3)
C7	0.040 (2)	0.029 (2)	0.042 (3)	0.0047 (18)	0.009 (2)	0.003 (2)
C8	0.031 (2)	0.038 (3)	0.046 (3)	0.0073 (18)	0.0081 (19)	−0.003 (2)
C9	0.037 (2)	0.042 (3)	0.037 (2)	0.0061 (19)	0.0012 (19)	0.002 (2)
C10	0.034 (2)	0.034 (2)	0.036 (2)	0.0026 (17)	0.0050 (19)	0.0001 (19)
C11	0.039 (2)	0.048 (3)	0.037 (3)	0.003 (2)	0.006 (2)	−0.003 (2)
C12	0.035 (2)	0.058 (3)	0.048 (3)	0.006 (2)	0.011 (2)	−0.001 (2)
C13	0.047 (3)	0.058 (3)	0.046 (3)	0.003 (2)	0.015 (2)	0.004 (3)
C14	0.047 (3)	0.091 (4)	0.061 (4)	0.002 (3)	0.021 (3)	0.012 (4)
C15	0.037 (2)	0.040 (3)	0.039 (3)	−0.0050 (19)	0.009 (2)	0.007 (2)
O6	0.0373 (18)	0.066 (2)	0.064 (3)	−0.0017 (17)	−0.0051 (17)	−0.0037 (19)
C16	0.067 (4)	0.086 (5)	0.095 (5)	−0.017 (4)	0.010 (4)	0.005 (4)

Geometric parameters (Å, º) top

S1—O1	1.426 (3)	C7—C8	1.539 (7)
S1—O2	1.429 (3)	C7—C9	1.545 (7)
S1—N1	1.629 (4)	C10—C11	1.333 (7)
S1—C1	1.752 (5)	C10—C15	1.492 (7)
S2—C9	1.790 (5)	C11—C12	1.524 (7)
S2—C12	1.806 (5)	C11—C13	1.460 (7)
O3—C8	1.197 (6)	C13—C14	1.312 (8)
O4—C15	1.308 (6)	C2—H2	0.9300
O5—C15	1.212 (6)	C3—H3	0.9300
O4—H4A	0.8200	C4—H4	0.9300
O6—C16	1.411 (8)	C5—H5	0.9300
O6—H6A	0.8200	C6—H6	0.9300
N1—C7	1.454 (6)	C7—H7	0.9800
N2—C8	1.377 (6)	C9—H9	0.9800
N2—C10	1.395 (6)	C12—H12B	0.9700
N2—C9	1.468 (6)	C12—H12A	0.9700
N1—H1	0.8600	C13—H13	0.9300
C1—C6	1.375 (7)	C14—H14B	0.9300
C1—C2	1.373 (8)	C14—H14A	0.9300
C2—C3	1.382 (10)	C16—H16A	0.9600
C3—C4	1.356 (12)	C16—H16B	0.9600
C4—C5	1.378 (11)	C16—H16C	0.9600
C5—C6	1.374 (10)

S2···N1	3.111 (4)	C16···O5^v	3.388 (7)
S2···H1	2.7600	C16···O3	3.397 (7)
O1···C7ⁱ	3.037 (6)	C1···H5^vii	3.0600
O1···C8ⁱ	3.044 (6)	C11···H14B^viii	2.9900
O2···C12ⁱⁱ	3.327 (6)	C12···H14A	2.5700
O3···O5	3.167 (5)	C12···H4^ix	3.0000
O3···N1	3.243 (5)	C14···H3^x	3.0300
O3···C15	3.210 (6)	C14···H12A	2.9900
O3···O6	2.799 (5)	C14···H13^viii	2.9000
O3···C16	3.397 (7)	C14···H12B	2.6500
O4···O6ⁱⁱⁱ	2.575 (5)	C15···H1^iv	3.0000
O4···C13	2.982 (6)	C15···H13	2.6500
O5···N2	2.801 (5)	C16···H4A^v	2.6800
O5···C8	3.215 (6)	H1···S2	2.7600
O5···O3	3.167 (5)	H1···C15ⁱ	3.0000
O5···C16ⁱⁱⁱ	3.388 (7)	H1···O5ⁱ	2.3000
O5···N1^iv	2.888 (5)	H2···O1	2.5300
O6···C15^v	3.348 (6)	H2···O3ⁱ	2.8100
O6···O4^v	2.575 (5)	H3···H14A^xi	2.5700
O6···O3	2.799 (5)	H3···C14^xi	3.0300
O1···H7ⁱ	2.3400	H4···C12^xii	3.0000
O1···H2	2.5300	H4A···O6ⁱⁱⁱ	1.7600
O2···H12Aⁱⁱ	2.4600	H4A···C16ⁱⁱⁱ	2.6800
O2···H6	2.6600	H4A···H6Aⁱⁱⁱ	2.3200
O2···H9ⁱⁱ	2.7000	H5···C1^xiii	3.0600
O2···H7	2.4500	H6···O2	2.6600
O3···H2^iv	2.8100	H6A···O3	2.0000
O3···H16B^v	2.8500	H6A···H4A^v	2.3200
O3···H6A	2.0000	H7···O1^iv	2.3400
O4···H13	2.4400	H7···O2	2.4500
O5···H1^iv	2.3000	H9···O2^vi	2.7000
O5···H16C	2.7000	H12A···C14	2.9900
O5···H16Bⁱⁱⁱ	2.8800	H12A···H14A	2.5600
O6···H4A^v	1.7600	H12A···O2^vi	2.4600
N1···S2	3.111 (4)	H12B···C14	2.6500
N1···O3	3.243 (5)	H12B···H14A	2.1400
N1···N2	3.274 (5)	H13···C14^xiv	2.9000
N1···O5ⁱ	2.888 (5)	H13···C15	2.6500
N2···O5	2.801 (5)	H13···O4	2.4400
N2···N1	3.274 (5)	H14A···H3^x	2.5700
C7···O1^iv	3.037 (6)	H14A···C12	2.5700
C8···O5	3.215 (6)	H14A···H12A	2.5600
C8···O1^iv	3.044 (6)	H14A···H12B	2.1400
C12···O2^vi	3.327 (6)	H14B···C11^xiv	2.9900
C13···O4	2.982 (6)	H16B···O3ⁱⁱⁱ	2.8500
C15···O6ⁱⁱⁱ	3.348 (6)	H16B···O5^v	2.8800
C15···O3	3.210 (6)	H16C···O5	2.7000

O1—S1—O2	120.4 (2)	S2—C12—C11	117.0 (4)
O1—S1—N1	105.6 (2)	C11—C13—C14	125.5 (5)
O1—S1—C1	107.8 (2)	O4—C15—O5	123.3 (5)
O2—S1—N1	107.1 (2)	O5—C15—C10	122.7 (5)
O2—S1—C1	108.0 (2)	O4—C15—C10	114.0 (4)
N1—S1—C1	107.4 (2)	C1—C2—H2	120.00
C9—S2—C12	93.0 (2)	C3—C2—H2	120.00
C15—O4—H4A	109.00	C2—C3—H3	120.00
C16—O6—H6A	110.00	C4—C3—H3	120.00
S1—N1—C7	118.8 (3)	C5—C4—H4	120.00
C9—N2—C10	124.6 (4)	C3—C4—H4	120.00
C8—N2—C9	94.8 (4)	C4—C5—H5	120.00
C8—N2—C10	135.5 (4)	C6—C5—H5	120.00
C7—N1—H1	121.00	C5—C6—H6	120.00
S1—N1—H1	121.00	C1—C6—H6	120.00
C2—C1—C6	120.2 (5)	N1—C7—H7	111.00
S1—C1—C2	119.2 (4)	C9—C7—H7	111.00
S1—C1—C6	120.6 (4)	C8—C7—H7	111.00
C1—C2—C3	119.9 (6)	N2—C9—H9	113.00
C2—C3—C4	119.7 (7)	C7—C9—H9	113.00
C3—C4—C5	120.8 (7)	S2—C9—H9	113.00
C4—C5—C6	119.7 (6)	S2—C12—H12B	108.00
C1—C6—C5	119.7 (5)	C11—C12—H12A	108.00
N1—C7—C9	118.3 (4)	S2—C12—H12A	108.00
N1—C7—C8	117.5 (4)	H12A—C12—H12B	107.00
C8—C7—C9	85.5 (3)	C11—C12—H12B	108.00
O3—C8—C7	136.8 (5)	C11—C13—H13	117.00
O3—C8—N2	132.1 (5)	C14—C13—H13	117.00
N2—C8—C7	91.1 (4)	C13—C14—H14B	120.00
S2—C9—C7	117.9 (3)	H14A—C14—H14B	120.00
N2—C9—C7	87.5 (3)	C13—C14—H14A	120.00
S2—C9—N2	109.6 (3)	O6—C16—H16A	109.00
N2—C10—C11	121.0 (4)	O6—C16—H16B	109.00
N2—C10—C15	112.4 (4)	O6—C16—H16C	109.00
C11—C10—C15	126.4 (4)	H16A—C16—H16B	109.00
C10—C11—C13	121.6 (4)	H16A—C16—H16C	110.00
C10—C11—C12	122.1 (4)	H16B—C16—H16C	109.00
C12—C11—C13	116.3 (4)

O1—S1—N1—C7	−171.2 (4)	C6—C1—C2—C3	−1.9 (9)
O2—S1—N1—C7	−41.7 (4)	S1—C1—C2—C3	176.6 (5)
C1—S1—N1—C7	74.0 (4)	C2—C1—C6—C5	0.1 (9)
O1—S1—C1—C2	−17.8 (5)	C1—C2—C3—C4	2.6 (11)
O2—S1—C1—C2	−149.4 (4)	C2—C3—C4—C5	−1.6 (12)
N1—S1—C1—C2	95.5 (5)	C3—C4—C5—C6	−0.1 (11)
O1—S1—C1—C6	160.6 (4)	C4—C5—C6—C1	0.9 (10)
O2—S1—C1—C6	29.1 (5)	C8—C7—C9—N2	7.4 (3)
N1—S1—C1—C6	−86.0 (5)	N1—C7—C8—N2	−127.6 (4)
C12—S2—C9—N2	58.9 (3)	C9—C7—C8—O3	171.1 (6)
C12—S2—C9—C7	156.7 (4)	N1—C7—C8—O3	51.4 (8)
C9—S2—C12—C11	−48.2 (4)	N1—C7—C9—S2	15.4 (6)
S1—N1—C7—C9	148.9 (3)	N1—C7—C9—N2	126.3 (4)
S1—N1—C7—C8	−110.7 (4)	C8—C7—C9—S2	−103.5 (3)
C10—N2—C8—O3	−17.0 (9)	C9—C7—C8—N2	−7.9 (3)
C9—N2—C8—C7	8.3 (3)	N2—C10—C11—C12	9.9 (7)
C9—N2—C10—C15	−168.8 (4)	N2—C10—C11—C13	−165.8 (4)
C8—N2—C10—C15	43.6 (7)	C15—C10—C11—C13	8.4 (8)
C9—N2—C8—O3	−170.7 (5)	N2—C10—C15—O4	−138.0 (4)
C10—N2—C9—S2	−47.4 (5)	C15—C10—C11—C12	−175.9 (4)
C8—N2—C9—C7	−8.3 (3)	C11—C10—C15—O4	47.3 (6)
C10—N2—C9—C7	−166.2 (4)	C11—C10—C15—O5	−135.0 (5)
C10—N2—C8—C7	162.1 (5)	N2—C10—C15—O5	39.6 (6)
C9—N2—C10—C11	6.2 (7)	C10—C11—C12—S2	18.3 (6)
C8—N2—C10—C11	−141.5 (5)	C10—C11—C13—C14	176.6 (5)
C8—N2—C9—S2	110.5 (3)	C12—C11—C13—C14	0.6 (8)
S1—C1—C6—C5	−178.3 (5)	C13—C11—C12—S2	−165.8 (4)

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+2; (iii) −x, y+1/2, −z+1; (iv) x, y+1, z; (v) −x, y−1/2, −z+1; (vi) −x+1, y+1/2, −z+2; (vii) −x, y−1/2, −z+2; (viii) −x+1, y−1/2, −z+1; (ix) x+1, y, z; (x) x+1, y+1, z; (xi) x−1, y−1, z; (xii) x−1, y, z; (xiii) −x, y+1/2, −z+2; (xiv) −x+1, y+1/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S2	0.86	2.76	3.111 (4)	106
N1—H1···O5ⁱ	0.86	2.30	2.888 (5)	126
O4—H4A···O6ⁱⁱⁱ	0.82	1.76	2.575 (5)	171
O6—H6A···O3	0.82	2.00	2.799 (5)	166
C2—H2···O1	0.93	2.53	2.888 (7)	103
C7—H7···O1^iv	0.98	2.34	3.037 (6)	127
C7—H7···O2	0.98	2.45	2.906 (6)	108
C12—H12A···O2^vi	0.97	2.46	3.327 (6)	148
C13—H13···O4	0.93	2.44	2.982 (6)	117

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₄N₂O₅S₂·CH₄O
M_r	398.46
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	12.0000 (2), 6.0964 (8), 13.602 (2)
β (°)	109.412 (7)
V (Å³)	938.51 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.31 × 0.28 × 0.11

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9995, 3862, 2296
R_int	0.125
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.120, 0.96
No. of reflections	3862
No. of parameters	238
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.25
Absolute structure	Flack (1983), 1498 Freidel pairs
Absolute structure parameter	0.01 (10)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).