Ethyl (E)-3-hy­droxy-2-{N-[2-(thio­phen-2-yl)ethen­yl]carbamo­yl}but-2-enoate

Liu, B.-S.; Zhao, S.-Y.

doi:10.1107/S1600536812028176

organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page o2284

https://doi.org/10.1107/S1600536812028176

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Ethyl (E)-3-hydroxy-2-{N-[2-(thiophen-2-yl)ethenyl]carbamoyl}but-2-enoate

Bao-Shuo Liu ^a and Sheng-Yin Zhao ^a ^*

^aCollege of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, People's Republic of China
^*Correspondence e-mail: syzhao8@dhu.edu.cn

(Received 12 June 2012; accepted 21 June 2012; online 30 June 2012)

In the title compound, C₁₃H₁₅NO₄S, there are two independent but conformationally similar molecules in the asymmetric unit, both having an E conformation of the side-chain C=C group. Intramolecular N—H⋯O and O—H⋯O hydrogen-bonding interactions are present in both molecules. In the crystal, one of the molecule types is linked through intermolecular hydroxy–ketone O—H⋯O interactions, forming one-dimensional chains extending along [010], whereas the other molecule type shows no associations.

Related literature

For applications of 4-hydroxy-2-pyridones, see: Buisson et al. (1996 ); Jessen & Gademann (2010 ). For general background to the synthesis, see: Rigby & Burkhardt (1986 ); Rigby & Qabar (1989 ). For the structure of a similar compound, see: Zhao & Huang (2012 ).

Experimental

Crystal data

C₁₃H₁₅NO₄S
M_r = 281.33
Monoclinic, P 2₁ /n
a = 14.0185 (15) Å
b = 13.1232 (14) Å
c = 15.0141 (16) Å
β = 96.853 (2)°
V = 2742.4 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.32 × 0.21 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.394, T_max = 1.000
15596 measured reflections
5099 independent reflections
3538 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.179
S = 1.05
5099 reflections
357 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1′—H1′A⋯O3′	0.77 (3)	1.98 (3)	2.615 (3)	139 (3)
N1—H1A⋯O3	0.68 (3)	2.10 (3)	2.637 (3)	137 (3)
O2′—H2′⋯O1′	0.82	1.65	2.399 (3)	152
O2—H2A⋯O1	0.82	1.67	2.419 (3)	151
O2—H2A⋯O3ⁱ	0.82	2.48	2.936 (3)	117
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812028176/zs2216sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812028176/zs2216Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812028176/zs2216Isup3.cml

checkCIF report

Comment top

The derivatives of 4-hydroxy-2-pyridones exhibit a wide range of biological activities (Buisson et al., 1996; Jessen & Gademann, 2010). The title compound, C₁₃H₁₅NO₄S, is an important intermediate in the synthesis of 4-hydroxy-2-pyridone derivatives (Rigby & Burkhardt, 1986; Rigby & Qabar, 1989). In the title compound, there are two independent but conformationally similar molecules in the asymmetric unit (Figs. 1 and 2), both of which have an E configuration of the side chain C5═C6. The molecular conformation is stabilized by intramolecular N—H···O_ketone and hydroxyl O—H···O_ketone hydrogen bonds (Table 1, Figs. 1 and 2).

In the crystal, only one of the molecule types is linked through intermolecular hydroxyl O—H···O_ketone interactions forming one-dimensional chain structures extending along (010) (Fig. 3), whereas the other molecule type is unassociated. The thiophene rings have normal hydrophobic contacts without any stacking interactions. For the structure of a similar compound, see Zhao & Huang (2012).

Related literature top

For applications of 4-hydroxy-2-pyridones, see: Buisson et al. (1996); Jessen & Gademann (2010). For general background to the synthesis, see: Rigby & Burkhardt (1986); Rigby & Qabar (1989). For the structure of a similar compound, see: Zhao & Huang (2012).

Experimental top

To an ice-cooled solution of 3-(2-thienyl)acrylic acid (5.0 g, 32.5 mmol) in 70 ml of ethyl acetate was added triethylamine (4.3 g, 42.2 mmol) and diphenyl phosphorazidate (DPPA, 11.6 g, 42.2 mmol). The solution was stirred at room temperature for 4 h. The acyl azide product was washed by dilution with cold water. The organic layers were dried over MgSO₄, and the solvent was removed under reduced pressure (< 318 K). The acyl azide was dissolved in 50 ml of benzene and heated under reflux until azide decomposition was complete. The reaction mixture was then cooled to 273 K and ethyl sodio-acetoacetate [prepared from ethyl acetoacetate (5.07 g, 39.0 mmol) and sodium hydride (1.1 g, 60% dispersion in oil, 45.5 mmol) in toluene (100 ml) at 273 K] was added. After warming to room temperature for 2 h, the mixture was quenched with saturated aqueous ammonium chloride solution, rinsed with brine, and dried over MgSO₄. The solvent was removed in vacuo to give green crystals: 5.57 g, yield, 61.0% (m.p. 366–368 K). 1H NMR (400 MHz, chloroform-d) 1.37 (t, J = 7.1 Hz, 3H, CH₃), 2.47 (s, 3H, CH₃), 4.29 (q, J = 7.1 Hz, 2H, CH₂), 6.41 (d, J = 14.5 Hz, 1H, =CH), 6.91 (s, 1H, Ar—H), 6.93 (d, J = 4.4 Hz, 1H, Ar—H), 7.10 (d, J = 4.9 Hz, 1H, Ar—H), 7.41 (dd, J = 14.3, 10.8 Hz, 1H, =CH), 11.06 (d, J = 10.0 Hz, 1H, NH), 18.04 (s, 1H, OH). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation at room temperature from a solution in a mixture of hexane and ethyl acetate (10:1).

Structure description top

For applications of 4-hydroxy-2-pyridones, see: Buisson et al. (1996); Jessen & Gademann (2010). For general background to the synthesis, see: Rigby & Burkhardt (1986); Rigby & Qabar (1989). For the structure of a similar compound, see: Zhao & Huang (2012).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The atom-numbering scheme of the first molecule in the asymmetric unit of the title compound, with displacement ellipsoids drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. The atom-numbering scheme of the second molecule in the asymmetric unit of the title compound.
	Fig. 3. Molecular packing of the title compound viewed down the a axis of the unit cell, with O—H···O interactions shown as dashed lines.

Ethyl (E)-3-hydroxy-2-{N-[2- (thiophen-2-yl)ethenyl]carbamoyl}but-2-enoate top

Crystal data top

C₁₃H₁₅NO₄S	F(000) = 1184
M_r = 281.33	D_x = 1.363 Mg m⁻³
Monoclinic, P2₁/n	Melting point = 366–368 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 14.0185 (15) Å	Cell parameters from 3746 reflections
b = 13.1232 (14) Å	θ = 4.9–26.5°
c = 15.0141 (16) Å	µ = 0.25 mm⁻¹
β = 96.853 (2)°	T = 293 K
V = 2742.4 (5) Å³	Prismatic, white
Z = 8	0.32 × 0.21 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5099 independent reflections
Radiation source: fine-focus sealed tube	3538 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
φ and ω scans	θ_max = 25.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −15→16
T_min = 0.394, T_max = 1.000	k = −15→14
15596 measured reflections	l = −18→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.1017P)² + 0.3594P] where P = (F_o² + 2F_c²)/3
5099 reflections	(Δ/σ)_max < 0.001
357 parameters	Δρ_max = 0.42 e Å⁻³
1 restraint	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₁₃H₁₅NO₄S	V = 2742.4 (5) Å³
M_r = 281.33	Z = 8
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.0185 (15) Å	µ = 0.25 mm⁻¹
b = 13.1232 (14) Å	T = 293 K
c = 15.0141 (16) Å	0.32 × 0.21 × 0.15 mm
β = 96.853 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5099 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	3538 reflections with I > 2σ(I)
T_min = 0.394, T_max = 1.000	R_int = 0.061
15596 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	1 restraint
wR(F²) = 0.179	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.42 e Å⁻³
5099 reflections	Δρ_min = −0.34 e Å⁻³
357 parameters

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	0.36218 (6)	0.30430 (6)	0.06353 (5)	0.0674 (3)
S1'	0.60812 (7)	0.54606 (7)	0.67909 (7)	0.0873 (3)
N1	0.64877 (16)	0.25510 (18)	0.23340 (16)	0.0511 (6)
N1'	0.89786 (17)	0.6539 (2)	0.81282 (16)	0.0570 (6)
O1	0.68462 (15)	0.41967 (13)	0.22337 (15)	0.0716 (6)
O2	0.83238 (15)	0.49138 (13)	0.29706 (14)	0.0659 (6)
H2A	0.7772	0.4877	0.2721	0.099*
O3	0.78402 (14)	0.13804 (13)	0.31666 (15)	0.0682 (6)
O4	0.93063 (13)	0.20136 (12)	0.34348 (13)	0.0594 (5)
O1'	0.94002 (16)	0.49320 (16)	0.84332 (16)	0.0792 (7)
O2'	1.09020 (16)	0.44802 (15)	0.92784 (17)	0.0805 (7)
H2'	1.0350	0.4438	0.9029	0.121*
O3'	1.02266 (15)	0.79503 (14)	0.86837 (14)	0.0699 (6)
O4'	1.16883 (13)	0.74930 (13)	0.92788 (12)	0.0583 (5)
C1	0.2546 (2)	0.2520 (2)	0.02830 (19)	0.0658 (8)
H1	0.2065	0.2853	−0.0086	0.079*
C2	0.2461 (2)	0.1575 (2)	0.0591 (2)	0.0702 (8)
H2	0.1909	0.1187	0.0447	0.084*
C3	0.32914 (19)	0.1194 (2)	0.11653 (18)	0.0571 (7)
H3	0.3346	0.0561	0.1444	0.068*
C4	0.40153 (18)	0.19769 (18)	0.12237 (17)	0.0489 (6)
C5	0.49619 (18)	0.19051 (18)	0.17316 (17)	0.0512 (6)
H5	0.5141	0.1279	0.1989	0.061*
C6	0.55842 (19)	0.26513 (19)	0.18571 (17)	0.0503 (6)
H6	0.5409	0.3285	0.1612	0.060*
C7	0.71066 (19)	0.33179 (17)	0.25083 (17)	0.0492 (6)
C8	0.80519 (18)	0.31539 (16)	0.29962 (16)	0.0442 (6)
C9	0.86181 (18)	0.40078 (18)	0.32367 (17)	0.0483 (6)
C10	0.9549 (2)	0.4027 (2)	0.3815 (2)	0.0631 (8)
H10A	1.0050	0.3813	0.3474	0.095*
H10B	0.9522	0.3574	0.4313	0.095*
H10C	0.9678	0.4707	0.4032	0.095*
C11	0.83634 (18)	0.21138 (17)	0.32113 (16)	0.0470 (6)
C12	0.9659 (2)	0.0986 (2)	0.3595 (2)	0.0732 (9)
H12A	0.9616	0.0610	0.3035	0.088*
H12B	0.9279	0.0634	0.3998	0.088*
C13	1.0655 (3)	0.1052 (3)	0.3993 (3)	0.1086 (15)
H13A	1.1034	0.1357	0.3572	0.163*
H13B	1.0894	0.0381	0.4145	0.163*
H13C	1.0694	0.1463	0.4526	0.163*
C1'	0.5056 (3)	0.5833 (4)	0.6165 (3)	0.0967 (13)
H1'	0.4553	0.5394	0.5973	0.116*
C2'	0.5052 (2)	0.6825 (4)	0.5977 (2)	0.0845 (11)
H2'1	0.4546	0.7156	0.5637	0.101*
C3'	0.5891 (2)	0.7312 (3)	0.63484 (19)	0.0637 (7)
H3'	0.6001	0.8005	0.6283	0.076*
C4'	0.6534 (2)	0.6673 (2)	0.68161 (17)	0.0557 (7)
C5'	0.7466 (2)	0.6926 (2)	0.72761 (18)	0.0576 (7)
H5'	0.7641	0.7610	0.7286	0.069*
C6'	0.8093 (2)	0.6281 (2)	0.76828 (18)	0.0576 (7)
H6'	0.7925	0.5595	0.7669	0.069*
C7'	0.9618 (2)	0.5860 (2)	0.84934 (18)	0.0556 (7)
C8'	1.05502 (19)	0.61925 (19)	0.89353 (17)	0.0501 (6)
C9'	1.1163 (2)	0.5435 (2)	0.93281 (19)	0.0594 (7)
C10'	1.2130 (2)	0.5563 (2)	0.9827 (2)	0.0771 (9)
H10D	1.2297	0.4963	1.0177	0.116*
H10E	1.2130	0.6143	1.0218	0.116*
H10F	1.2590	0.5667	0.9411	0.116*
C11'	1.07879 (19)	0.7279 (2)	0.89515 (16)	0.0505 (6)
C12'	1.1946 (2)	0.8560 (2)	0.93642 (19)	0.0609 (7)
H12C	1.1504	0.8917	0.9706	0.073*
H12D	1.1917	0.8873	0.8776	0.073*
C13'	1.2938 (2)	0.8616 (2)	0.9834 (2)	0.0691 (8)
H13D	1.2952	0.8330	1.0423	0.104*
H13E	1.3140	0.9315	0.9880	0.104*
H13F	1.3364	0.8240	0.9501	0.104*
H1A	0.661 (2)	0.208 (2)	0.2506 (19)	0.055 (9)*
H1'A	0.912 (2)	0.711 (2)	0.818 (2)	0.066 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0635 (5)	0.0618 (5)	0.0737 (5)	−0.0007 (3)	−0.0051 (4)	0.0088 (3)
S1'	0.0765 (6)	0.0780 (6)	0.1028 (7)	−0.0186 (5)	−0.0078 (5)	0.0014 (5)
N1	0.0471 (13)	0.0350 (12)	0.0689 (15)	0.0038 (10)	−0.0025 (10)	0.0029 (10)
N1'	0.0489 (14)	0.0548 (15)	0.0644 (15)	0.0007 (11)	−0.0052 (11)	−0.0071 (11)
O1	0.0608 (13)	0.0382 (10)	0.1093 (16)	0.0041 (9)	−0.0166 (11)	0.0125 (10)
O2	0.0665 (14)	0.0344 (9)	0.0914 (15)	−0.0025 (8)	−0.0122 (11)	0.0027 (9)
O3	0.0576 (12)	0.0332 (9)	0.1070 (16)	−0.0027 (8)	−0.0186 (11)	0.0007 (9)
O4	0.0492 (11)	0.0376 (9)	0.0874 (13)	0.0054 (8)	−0.0084 (10)	−0.0022 (8)
O1'	0.0706 (14)	0.0529 (12)	0.1078 (17)	−0.0076 (10)	−0.0155 (12)	−0.0068 (11)
O2'	0.0668 (15)	0.0505 (12)	0.1185 (19)	0.0000 (10)	−0.0117 (13)	0.0073 (11)
O3'	0.0685 (14)	0.0478 (10)	0.0869 (14)	0.0034 (9)	−0.0175 (11)	0.0026 (9)
O4'	0.0521 (11)	0.0458 (10)	0.0752 (12)	−0.0046 (8)	−0.0004 (9)	−0.0048 (8)
C1	0.0579 (18)	0.0688 (19)	0.0661 (18)	0.0031 (14)	−0.0113 (14)	−0.0008 (14)
C2	0.0564 (18)	0.0648 (18)	0.083 (2)	−0.0062 (14)	−0.0199 (14)	−0.0006 (15)
C3	0.0506 (15)	0.0484 (14)	0.0669 (17)	0.0010 (12)	−0.0149 (12)	−0.0134 (12)
C4	0.0504 (15)	0.0441 (13)	0.0510 (14)	0.0044 (11)	0.0007 (12)	−0.0056 (10)
C5	0.0494 (15)	0.0413 (13)	0.0615 (16)	0.0053 (11)	0.0007 (12)	−0.0027 (11)
C6	0.0489 (15)	0.0428 (13)	0.0575 (15)	0.0068 (11)	−0.0009 (12)	0.0005 (11)
C7	0.0515 (16)	0.0361 (12)	0.0592 (15)	0.0015 (11)	0.0036 (12)	−0.0002 (10)
C8	0.0481 (15)	0.0336 (12)	0.0498 (13)	0.0017 (10)	0.0017 (11)	−0.0035 (9)
C9	0.0529 (16)	0.0374 (13)	0.0541 (15)	−0.0004 (11)	0.0042 (12)	−0.0021 (10)
C10	0.0678 (19)	0.0431 (14)	0.0742 (18)	−0.0095 (13)	−0.0092 (15)	−0.0037 (12)
C11	0.0494 (15)	0.0362 (12)	0.0526 (14)	0.0016 (11)	−0.0051 (11)	−0.0044 (10)
C12	0.0647 (19)	0.0408 (15)	0.107 (2)	0.0112 (13)	−0.0169 (17)	−0.0062 (14)
C13	0.068 (2)	0.067 (2)	0.179 (4)	0.0143 (18)	−0.034 (3)	−0.007 (2)
C1'	0.065 (2)	0.137 (4)	0.085 (2)	−0.029 (2)	−0.0066 (18)	−0.025 (2)
C2'	0.058 (2)	0.125 (3)	0.067 (2)	0.008 (2)	−0.0069 (16)	−0.008 (2)
C3'	0.0518 (17)	0.0746 (19)	0.0628 (17)	0.0080 (14)	−0.0007 (13)	−0.0031 (14)
C4'	0.0528 (17)	0.0661 (17)	0.0484 (15)	−0.0024 (13)	0.0063 (12)	−0.0088 (12)
C5'	0.0533 (17)	0.0620 (16)	0.0573 (16)	−0.0024 (13)	0.0055 (13)	−0.0075 (13)
C6'	0.0547 (17)	0.0616 (16)	0.0548 (16)	−0.0010 (13)	−0.0008 (13)	−0.0072 (12)
C7'	0.0558 (17)	0.0484 (15)	0.0612 (17)	0.0003 (12)	0.0021 (13)	−0.0056 (12)
C8'	0.0464 (15)	0.0470 (13)	0.0560 (15)	0.0023 (11)	0.0020 (12)	−0.0026 (11)
C9'	0.0541 (17)	0.0515 (16)	0.0710 (18)	0.0005 (12)	0.0014 (14)	0.0016 (13)
C10'	0.0569 (19)	0.0627 (18)	0.106 (3)	0.0054 (15)	−0.0114 (17)	0.0150 (17)
C11'	0.0514 (16)	0.0523 (14)	0.0464 (14)	−0.0004 (12)	0.0001 (12)	−0.0022 (11)
C12'	0.0695 (19)	0.0465 (15)	0.0656 (17)	−0.0104 (13)	0.0035 (14)	−0.0012 (12)
C13'	0.0647 (19)	0.0686 (19)	0.073 (2)	−0.0158 (15)	0.0051 (15)	−0.0085 (15)

Geometric parameters (Å, º) top

S1—C1	1.684 (3)	C8—C11	1.458 (3)
S1—C4	1.710 (3)	C9—C10	1.478 (3)
S1'—C1'	1.692 (4)	C10—H10A	0.9600
S1'—C4'	1.712 (3)	C10—H10B	0.9600
N1—C7	1.334 (3)	C10—H10C	0.9600
N1—C6	1.385 (3)	C12—C13	1.454 (4)
N1—H1A	0.68 (3)	C12—H12A	0.9700
N1'—C7'	1.335 (4)	C12—H12B	0.9700
N1'—C6'	1.381 (3)	C13—H13A	0.9600
N1'—H1'A	0.77 (3)	C13—H13B	0.9600
O1—C7	1.264 (3)	C13—H13C	0.9600
O2—C9	1.305 (3)	C1'—C2'	1.332 (6)
O2—H2A	0.8200	C1'—H1'	0.9300
O3—C11	1.207 (3)	C2'—C3'	1.396 (4)
O4—C11	1.331 (3)	C2'—H2'1	0.9300
O4—C12	1.447 (3)	C3'—C4'	1.363 (4)
O1'—C7'	1.256 (3)	C3'—H3'	0.9300
O2'—C9'	1.304 (3)	C4'—C5'	1.442 (4)
O2'—H2'	0.8200	C5'—C6'	1.316 (4)
O3'—C11'	1.217 (3)	C5'—H5'	0.9300
O4'—C11'	1.329 (3)	C6'—H6'	0.9300
O4'—C12'	1.448 (3)	C7'—C8'	1.460 (4)
C1—C2	1.334 (4)	C8'—C9'	1.398 (4)
C1—H1	0.9300	C8'—C11'	1.464 (4)
C2—C3	1.452 (4)	C9'—C10'	1.478 (4)
C2—H2	0.9300	C10'—H10D	0.9600
C3—C4	1.439 (4)	C10'—H10E	0.9600
C3—H3	0.9300	C10'—H10F	0.9600
C4—C5	1.453 (3)	C12'—C13'	1.484 (4)
C5—C6	1.310 (4)	C12'—H12C	0.9700
C5—H5	0.9300	C12'—H12D	0.9700
C6—H6	0.9300	C13'—H13D	0.9600
C7—C8	1.452 (3)	C13'—H13E	0.9600
C8—C9	1.396 (3)	C13'—H13F	0.9600

C1—S1—C4	92.87 (14)	C12—C13—H13A	109.5
C1'—S1'—C4'	91.8 (2)	C12—C13—H13B	109.5
C7—N1—C6	124.3 (2)	H13A—C13—H13B	109.5
C7—N1—H1A	119 (3)	C12—C13—H13C	109.5
C6—N1—H1A	117 (3)	H13A—C13—H13C	109.5
C7'—N1'—C6'	123.8 (3)	H13B—C13—H13C	109.5
C7'—N1'—H1'A	117 (2)	C2'—C1'—S1'	112.5 (3)
C6'—N1'—H1'A	120 (2)	C2'—C1'—H1'	123.8
C9—O2—H2A	109.5	S1'—C1'—H1'	123.8
C11—O4—C12	116.3 (2)	C1'—C2'—C3'	112.3 (3)
C9'—O2'—H2'	109.5	C1'—C2'—H2'1	123.8
C11'—O4'—C12'	117.0 (2)	C3'—C2'—H2'1	123.8
C2—C1—S1	112.6 (2)	C4'—C3'—C2'	113.5 (3)
C2—C1—H1	123.7	C4'—C3'—H3'	123.3
S1—C1—H1	123.7	C2'—C3'—H3'	123.3
C1—C2—C3	115.3 (3)	C3'—C4'—C5'	127.6 (3)
C1—C2—H2	122.4	C3'—C4'—S1'	109.9 (2)
C3—C2—H2	122.4	C5'—C4'—S1'	122.5 (2)
C4—C3—C2	107.5 (2)	C6'—C5'—C4'	126.2 (3)
C4—C3—H3	126.3	C6'—C5'—H5'	116.9
C2—C3—H3	126.3	C4'—C5'—H5'	116.9
C3—C4—C5	125.4 (2)	C5'—C6'—N1'	125.3 (3)
C3—C4—S1	111.76 (19)	C5'—C6'—H6'	117.3
C5—C4—S1	122.84 (19)	N1'—C6'—H6'	117.3
C6—C5—C4	125.3 (2)	O1'—C7'—N1'	118.2 (3)
C6—C5—H5	117.3	O1'—C7'—C8'	121.3 (2)
C4—C5—H5	117.3	N1'—C7'—C8'	120.5 (2)
C5—C6—N1	123.8 (2)	C9'—C8'—C7'	116.8 (2)
C5—C6—H6	118.1	C9'—C8'—C11'	124.0 (2)
N1—C6—H6	118.1	C7'—C8'—C11'	119.2 (2)
O1—C7—N1	117.9 (2)	O2'—C9'—C8'	120.3 (3)
O1—C7—C8	120.7 (2)	O2'—C9'—C10'	111.9 (2)
N1—C7—C8	121.3 (2)	C8'—C9'—C10'	127.8 (3)
C9—C8—C7	117.9 (2)	C9'—C10'—H10D	109.5
C9—C8—C11	123.3 (2)	C9'—C10'—H10E	109.5
C7—C8—C11	118.8 (2)	H10D—C10'—H10E	109.5
O2—C9—C8	120.2 (2)	C9'—C10'—H10F	109.5
O2—C9—C10	112.8 (2)	H10D—C10'—H10F	109.5
C8—C9—C10	126.9 (2)	H10E—C10'—H10F	109.5
C9—C10—H10A	109.5	O3'—C11'—O4'	121.1 (2)
C9—C10—H10B	109.5	O3'—C11'—C8'	124.2 (2)
H10A—C10—H10B	109.5	O4'—C11'—C8'	114.6 (2)
C9—C10—H10C	109.5	O4'—C12'—C13'	107.5 (2)
H10A—C10—H10C	109.5	O4'—C12'—H12C	110.2
H10B—C10—H10C	109.5	C13'—C12'—H12C	110.2
O3—C11—O4	120.9 (2)	O4'—C12'—H12D	110.2
O3—C11—C8	124.8 (2)	C13'—C12'—H12D	110.2
O4—C11—C8	114.2 (2)	H12C—C12'—H12D	108.5
O4—C12—C13	107.8 (2)	C12'—C13'—H13D	109.5
O4—C12—H12A	110.2	C12'—C13'—H13E	109.5
C13—C12—H12A	110.2	H13D—C13'—H13E	109.5
O4—C12—H12B	110.2	C12'—C13'—H13F	109.5
C13—C12—H12B	110.2	H13D—C13'—H13F	109.5
H12A—C12—H12B	108.5	H13E—C13'—H13F	109.5

C4—S1—C1—C2	0.3 (3)	C4'—S1'—C1'—C2'	0.3 (3)
S1—C1—C2—C3	0.6 (4)	S1'—C1'—C2'—C3'	−0.4 (4)
C1—C2—C3—C4	−1.4 (4)	C1'—C2'—C3'—C4'	0.4 (4)
C2—C3—C4—C5	−179.8 (3)	C2'—C3'—C4'—C5'	179.7 (3)
C2—C3—C4—S1	1.6 (3)	C2'—C3'—C4'—S1'	−0.2 (3)
C1—S1—C4—C3	−1.2 (2)	C1'—S1'—C4'—C3'	−0.1 (2)
C1—S1—C4—C5	−179.8 (2)	C1'—S1'—C4'—C5'	−179.9 (2)
C3—C4—C5—C6	−172.9 (3)	C3'—C4'—C5'—C6'	−176.2 (3)
S1—C4—C5—C6	5.6 (4)	S1'—C4'—C5'—C6'	3.7 (4)
C4—C5—C6—N1	−178.9 (2)	C4'—C5'—C6'—N1'	−179.3 (3)
C7—N1—C6—C5	−176.1 (3)	C7'—N1'—C6'—C5'	−176.3 (3)
C6—N1—C7—O1	1.2 (4)	C6'—N1'—C7'—O1'	−0.4 (4)
C6—N1—C7—C8	−178.6 (2)	C6'—N1'—C7'—C8'	178.5 (3)
O1—C7—C8—C9	6.9 (4)	O1'—C7'—C8'—C9'	−3.4 (4)
N1—C7—C8—C9	−173.2 (2)	N1'—C7'—C8'—C9'	177.8 (3)
O1—C7—C8—C11	−173.1 (2)	O1'—C7'—C8'—C11'	177.1 (3)
N1—C7—C8—C11	6.7 (4)	N1'—C7'—C8'—C11'	−1.7 (4)
C7—C8—C9—O2	−4.7 (4)	C7'—C8'—C9'—O2'	1.1 (4)
C11—C8—C9—O2	175.3 (2)	C11'—C8'—C9'—O2'	−179.4 (3)
C7—C8—C9—C10	172.8 (3)	C7'—C8'—C9'—C10'	−178.8 (3)
C11—C8—C9—C10	−7.2 (4)	C11'—C8'—C9'—C10'	0.7 (5)
C12—O4—C11—O3	1.5 (4)	C12'—O4'—C11'—O3'	4.6 (4)
C12—O4—C11—C8	−175.9 (2)	C12'—O4'—C11'—C8'	−176.1 (2)
C9—C8—C11—O3	165.5 (3)	C9'—C8'—C11'—O3'	−173.0 (3)
C7—C8—C11—O3	−14.5 (4)	C7'—C8'—C11'—O3'	6.4 (4)
C9—C8—C11—O4	−17.2 (4)	C9'—C8'—C11'—O4'	7.7 (4)
C7—C8—C11—O4	162.8 (2)	C7'—C8'—C11'—O4'	−172.8 (2)
C11—O4—C12—C13	−169.1 (3)	C11'—O4'—C12'—C13'	173.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1′—H1′A···O3′	0.77 (3)	1.98 (3)	2.615 (3)	139 (3)
N1—H1A···O3	0.68 (3)	2.10 (3)	2.637 (3)	137 (3)
O2′—H2′···O1′	0.82	1.65	2.399 (3)	152
O2—H2A···O1	0.82	1.67	2.419 (3)	151
O2—H2A···O3ⁱ	0.82	2.48	2.936 (3)	117

Symmetry code: (i) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₅NO₄S
M_r	281.33
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	14.0185 (15), 13.1232 (14), 15.0141 (16)
β (°)	96.853 (2)
V (Å³)	2742.4 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.32 × 0.21 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.394, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	15596, 5099, 3538
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.179, 1.05
No. of reflections	5099
No. of parameters	357
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.34

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1'—H1'A···O3'	0.77 (3)	1.98 (3)	2.615 (3)	139 (3)
N1—H1A···O3	0.68 (3)	2.10 (3)	2.637 (3)	137 (3)
O2'—H2'···O1'	0.82	1.65	2.399 (3)	152
O2—H2A···O1	0.82	1.67	2.419 (3)	151
O2—H2A···O3ⁱ	0.82	2.48	2.936 (3)	117

Symmetry code: (i) −x+3/2, y+1/2, −z+1/2.

Acknowledgements

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 21072029) and the Shanghai Municipal Natural Science Foundation (grant No. 10ZR1400700).

References

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