Diethyl 2,3-dihydro­thieno[3,4-b]-1,4-dioxine-5,7-dicarboxyl­ate

Ono, K.; Tomura, M.; Saito, K.

doi:10.1107/S1600536808000937

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o468

doi:10.1107/S1600536808000937

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Diethyl 2,3-dihydrothieno[3,4-b]-1,4-dioxine-5,7-dicarboxylate

Katsuhiko Ono,^a ^* Masaaki Tomura ^b and Katsuhiro Saito ^a

^aDepartment of Materials Science and Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan, and ^bInstitute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan
^*Correspondence e-mail: ono.katsuhiko@nitech.ac.jp

(Received 22 December 2007; accepted 10 January 2008; online 18 January 2008)

The title compound, C₁₂H₁₄O₆S, is a dicarboxylic acid diethyl ester of 3,4-ethylenedioxythiophene, which is a component of electrically conductive poly(3,4-ethylenedioxythiophene) (PEDOT). The ethylene group is disordered over two sites with occupancy factors 0.64 and 0.36. Both the carbonyl groups are coplanar with the thiophene ring. The molecules form centrosymmetric dimers with an R₂²(12) coupling by intermolecular C—H⋯O hydrogen bonds [3.333 (5) Å] at the ethoxycarbonyl groups. The dimer units are arranged to form a ribbon-like molecular sheet.

Related literature

The title compound was synthesized as a precursor of 3,4-ethylenedioxythiophene, which is polymerized to afford PEDOT (Groenendaal et al., 2000 ; Pei et al., 1994 ). Synthetic methods for the title compound have been reported by: Coffey et al. (1996 ); Kumar et al. (1998 ); Zong et al. (2002 ); Caras-Quintero & Bäuerle (2002 ). For literature on related molecular structures, including a 3,4-ethylenedioxythiophene ring system, see: Sotzing et al. (1996 ); Abboud et al. (1998 ); Kumar et al. (1998). For related literature, see: Bernstein et al. (1995 ); Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₄O₆S
M_r = 286.30
Triclinic, $[P \overline 1]$
a = 4.6805 (8) Å
b = 8.3673 (17) Å
c = 17.351 (3) Å
α = 94.294 (7)°
β = 92.024 (9)°
γ = 105.641 (9)°
V = 651.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 295 (1) K
0.60 × 0.10 × 0.08 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer
Absorption correction: none
5181 measured reflections
2899 independent reflections
2300 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.069
wR(F²) = 0.176
S = 1.11
2899 reflections
193 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯O3ⁱ	0.96	2.66	3.333 (5)	127
C9—H9A⋯O3ⁱⁱ	0.96	2.62	3.523 (7)	157
C6B—H6B1⋯O5ⁱⁱⁱ	0.97	2.68	3.233 (12)	117
Symmetry codes: (i) -x+3, -y, -z; (ii) -x+2, -y, -z; (iii) x+1, y+1, z.

Data collection: CrystalClear (Rigaku/MSC, 2001 ); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000937/hg2368sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000937/hg2368Isup2.hkl

checkCIF report

Comment top

The title compound (I) has been prepared as a precursor of 3,4-ethylenedioxythiophene (Coffey et al., 1996; Kumar et al., 1998; Zong et al., 2002; Caras-Quintero & Bäuerle, 2002), which is polymerized by oxidizing agents to afford poly(3,4-ethylenedioxythiophene) (PEDOT). PEDOT shows high electrical conductivities and high stabilities in the oxidized states. Furthermore, the thin films of oxidized PEDOT are almost transparent. Therefore, these are used for organic electrodes in the study of electronic devices (Groenendaal et al., 2000; Pei et al., 1994). With regard to the hole-transporting abilities, the arrangement of 3,4-ethylenedioxythiophene units in film has attracted considerable attention. A few crystal structures including a 3,4-ethylenedioxythiophene ring system were reported (Sotzing et al., 1996; Abboud et al., 1998; Kumar et al., 1998). In this paper, we report the crystal structure of compound (I) that is a dicarboxylic acid diethyl ester of 3,4-ethylenedioxythiophene.

The compound (I) crystallizes in the P1 space group. The molecular structure is shown in Fig. 1. The ethylene moiety is disordered over two sites (O1—C5A—C6A—O2 and O1—C5B—C6B—O2) with occupancies of 0.36:0.64. The bond lengths and angles are all within expected ranges (Allen et al., 1987). Both the carbonyl moieties are planar to the thiophene ring. The molecules form a centrosymmetric dimer with a graph-set motif (Bernstein et al., 1995) of R₂²(12) by intermolecular C–H···O hydrogen bonds at the ethoxycarbonyl groups [C9–H9B···O3(–x + 3, –y, –z): 3.333 (5) Å]. The dimer units are arranged to form a ribbon-like molecular sheet along the b axis, as shown in Fig. 2. The ribbon-like molecular sheets stack to form a layer structure (Fig. 3).

Related literature top

The title compound was synthesized as a precursor of 3,4-ethylenedioxythiophene, which is polymerized to afford PEDOT (Groenendaal et al., 2000; Pei et al., 1994). Synthetic methods for the title compound have been reported by: Coffey et al. (1996); Kumar et al. (1998); Zong et al. (2002); Caras-Quintero & Bäuerle (2002). For literature on related molecular structures, including a 3,4-ethylenedioxythiophene ring system, see: Sotzing et al. (1996); Abboud et al. (1998); Kumar et al. (1998). For related literature, see: Bernstein et al. (1995); Allen et al. (1987); Pei et al. (1994).

Experimental top

The title compound (I) was prepared as follows: A solution of diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate (3.12 g, 12 mmol) and caesium fluoride (7.26 g, 48 mmol) in dry acetonitrile (200 ml) was stirred for 1 h under nitrogen. After addition of a solution of ethylene di(p-toluenesulfonate) (5.55 g, 15 mmol) in dry acetonitrile (100 ml), the reaction mixture was refluxed for 48 h. The reaction mixture was filtered and the precipitate was washed with acetonitrile. The filtrate was concentrated and the residue was chromatographed on alumina gel (CH₂Cl₂) and silica gel (CH₂Cl₂) to afford the compound of (I) (2.38 g, 69%) as colorless needles. Physical data for (I): m.p. 424–425 K; IR (KBr, cm^-1) 2998, 1698, 1454, 1377, 1302, 1098; ¹H NMR (CDCl₃, δ p.p.m): 1.37 (t, J = 7.1 Hz, 6H), 4.35 (q, J = 7.1 Hz, 4H), 4.40 (s, 4H); ¹³C NMR (CDCl₃, δ p.p.m): 14.2, 61.3, 64.7, 111.8, 144.9, 160.7; MS (EI): m/z 286 (M⁺), 241, 213, 169. Anal. Calcd for C₁₂H₁₄O₆S: C, 50.34; H, 4.93. Found: C, 50.50; H, 4.96. Colorless crystals of (I) suitable for X-ray analysis were obtained from a methanol solution.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalClear (Rigaku/MSC, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms and H atoms are shown as small spheres of arbitrary radii. The disordered atoms (C5B and C6B) are omitted for clarity.
	Fig. 2. The packing diagram of (I), ribbon-like molecular sheet.
	Fig. 3. The packing diagram of (I), packing mode of molecular sheets.

Diethyl 2,3-dihydrothieno[3,4-b]-1,4-dioxine-5,7-dicarboxylate top

Crystal data top

C₁₂H₁₄O₆S	Z = 2
M_r = 286.30	F(000) = 300
Triclinic, P1	D_x = 1.460 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 4.6805 (8) Å	Cell parameters from 1654 reflections
b = 8.3673 (17) Å	θ = 3.3–27.5°
c = 17.351 (3) Å	µ = 0.27 mm⁻¹
α = 94.294 (7)°	T = 295 K
β = 92.024 (9)°	Plate, colorless
γ = 105.641 (9)°	0.60 × 0.10 × 0.08 mm
V = 651.4 (2) Å³

Data collection top

Rigaku/MSC Mercury CCD diffractometer	2300 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.036
Graphite Monochromator monochromator	θ_max = 27.5°, θ_min = 3.3°
Detector resolution: 14.6199 pixels mm^-1	h = −4→6
ϕ and ω scans	k = −10→10
5181 measured reflections	l = −22→19
2899 independent reflections

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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0793P)² + 0.337P] where P = (F_o² + 2F_c²)/3
2899 reflections	(Δ/σ)_max < 0.001
193 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₂H₁₄O₆S	γ = 105.641 (9)°
M_r = 286.30	V = 651.4 (2) Å³
Triclinic, P1	Z = 2
a = 4.6805 (8) Å	Mo Kα radiation
b = 8.3673 (17) Å	µ = 0.27 mm⁻¹
c = 17.351 (3) Å	T = 295 K
α = 94.294 (7)°	0.60 × 0.10 × 0.08 mm
β = 92.024 (9)°

Data collection top

Rigaku/MSC Mercury CCD diffractometer	2300 reflections with I > 2σ(I)
5181 measured reflections	R_int = 0.036
2899 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.069	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.11	Δρ_max = 0.55 e Å⁻³
2899 reflections	Δρ_min = −0.26 e Å⁻³
193 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.

The methylene carbon atoms and the associated hydrogen atoms of the dioxine ring are disordered over two sites (O1—C5A—C6A—O2 and O1—C5B—C6B—O2) with occupancies of 0.36 (2):0.64 (2). The values were determined by refining site occupancies.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.86744 (17)	0.05411 (9)	0.23931 (5)	0.0487 (3)
O1	1.1659 (5)	0.5120 (3)	0.18957 (13)	0.0547 (6)
O2	0.7713 (5)	0.4829 (2)	0.31477 (12)	0.0501 (5)
O3	1.2360 (6)	0.0234 (3)	0.11029 (18)	0.0783 (8)
O4	1.4165 (6)	0.2967 (3)	0.09719 (14)	0.0649 (7)
O5	0.4735 (5)	−0.0297 (3)	0.36729 (15)	0.0632 (6)
O6	0.4318 (4)	0.2289 (3)	0.39704 (12)	0.0491 (5)
C1	1.0739 (6)	0.2137 (4)	0.19066 (17)	0.0430 (6)
C2	1.0364 (6)	0.3648 (3)	0.21764 (16)	0.0400 (6)
C3	0.8393 (6)	0.3508 (3)	0.27903 (15)	0.0377 (6)
C4	0.7311 (6)	0.1889 (3)	0.29702 (16)	0.0399 (6)
C5A	1.162 (5)	0.6525 (14)	0.2449 (14)	0.062 (5)	0.36 (2)
H5A1	1.2257	0.7562	0.2207	0.074*	0.36 (2)
H5A2	1.2966	0.6576	0.2893	0.074*	0.36 (2)
C6A	0.855 (5)	0.629 (2)	0.2697 (13)	0.059 (4)	0.36 (2)
H6A1	0.8417	0.7271	0.3011	0.070*	0.36 (2)
H6A2	0.7183	0.6125	0.2246	0.070*	0.36 (2)
C5B	1.018 (4)	0.6382 (11)	0.2131 (7)	0.065 (3)	0.64 (2)
H5B1	0.8276	0.6153	0.1843	0.078*	0.64 (2)
H5B2	1.1379	0.7469	0.2017	0.078*	0.64 (2)
C6B	0.971 (4)	0.6381 (10)	0.2987 (7)	0.063 (3)	0.64 (2)
H6B1	1.1603	0.6543	0.3272	0.076*	0.64 (2)
H6B2	0.8898	0.7292	0.3153	0.076*	0.64 (2)
C7	1.2491 (7)	0.1675 (4)	0.12851 (19)	0.0517 (7)
C8	1.5944 (10)	0.2624 (6)	0.0335 (2)	0.0806 (12)
H8A	1.7836	0.3470	0.0367	0.097*
H8B	1.6335	0.1552	0.0378	0.097*
C9	1.4402 (13)	0.2613 (7)	−0.0398 (3)	0.1016 (16)
H9A	1.2575	0.1739	−0.0439	0.152*
H9B	1.5623	0.2426	−0.0809	0.152*
H9C	1.3978	0.3666	−0.0435	0.152*
C10	0.5316 (6)	0.1166 (3)	0.35600 (17)	0.0444 (6)
C11	0.2365 (7)	0.1649 (4)	0.45733 (19)	0.0571 (8)
H11A	0.3405	0.1178	0.4951	0.069*
H11B	0.0649	0.0783	0.4352	0.069*
C12	0.1406 (9)	0.3054 (5)	0.4950 (2)	0.0747 (11)
H12A	0.3081	0.3833	0.5227	0.112*
H12B	−0.0094	0.2637	0.5303	0.112*
H12C	0.0612	0.3602	0.4562	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0565 (5)	0.0320 (4)	0.0588 (5)	0.0137 (3)	0.0039 (3)	0.0041 (3)
O1	0.0743 (14)	0.0356 (11)	0.0540 (13)	0.0104 (10)	0.0276 (10)	0.0088 (9)
O2	0.0703 (13)	0.0307 (10)	0.0490 (12)	0.0103 (9)	0.0232 (10)	0.0043 (8)
O3	0.0888 (18)	0.0575 (15)	0.095 (2)	0.0335 (14)	0.0233 (15)	−0.0121 (14)
O4	0.0793 (16)	0.0678 (16)	0.0562 (14)	0.0309 (13)	0.0280 (12)	0.0075 (12)
O5	0.0707 (14)	0.0373 (12)	0.0790 (17)	0.0050 (10)	0.0115 (12)	0.0213 (11)
O6	0.0515 (11)	0.0418 (11)	0.0513 (12)	0.0041 (9)	0.0154 (9)	0.0127 (9)
C1	0.0454 (15)	0.0401 (15)	0.0445 (16)	0.0144 (12)	0.0023 (12)	0.0004 (12)
C2	0.0462 (14)	0.0328 (13)	0.0396 (14)	0.0079 (11)	0.0048 (11)	0.0039 (11)
C3	0.0421 (13)	0.0317 (13)	0.0379 (14)	0.0079 (10)	0.0030 (10)	0.0028 (11)
C4	0.0429 (14)	0.0313 (13)	0.0444 (15)	0.0080 (11)	0.0017 (11)	0.0049 (11)
C5A	0.089 (10)	0.021 (4)	0.066 (9)	0.000 (5)	0.024 (7)	−0.007 (5)
C6A	0.089 (11)	0.029 (5)	0.059 (10)	0.016 (6)	0.017 (7)	0.004 (6)
C5B	0.109 (8)	0.036 (3)	0.056 (5)	0.023 (4)	0.038 (5)	0.013 (3)
C6B	0.100 (7)	0.026 (3)	0.055 (5)	0.002 (4)	0.036 (4)	0.004 (3)
C7	0.0530 (17)	0.0508 (18)	0.0554 (18)	0.0238 (14)	0.0030 (14)	−0.0049 (15)
C8	0.082 (3)	0.106 (3)	0.068 (3)	0.047 (2)	0.028 (2)	0.005 (2)
C9	0.154 (5)	0.099 (4)	0.071 (3)	0.066 (3)	0.027 (3)	0.006 (3)
C10	0.0441 (14)	0.0361 (14)	0.0488 (16)	0.0014 (11)	0.0009 (12)	0.0122 (12)
C11	0.0505 (17)	0.064 (2)	0.0530 (19)	0.0031 (15)	0.0139 (14)	0.0208 (16)
C12	0.073 (2)	0.079 (3)	0.062 (2)	0.003 (2)	0.0216 (18)	0.000 (2)

Geometric parameters (Å, º) top

S1—C4	1.716 (3)	C5A—H5A2	0.9700
S1—C1	1.720 (3)	C6A—H6A1	0.9700
O1—C2	1.352 (3)	C6A—H6A2	0.9700
O1—C5B	1.453 (8)	C5B—C6B	1.508 (18)
O1—C5A	1.466 (13)	C5B—H5B1	0.9700
O2—C3	1.345 (3)	C5B—H5B2	0.9700
O2—C6B	1.435 (9)	C6B—H6B1	0.9700
O2—C6A	1.468 (16)	C6B—H6B2	0.9700
O3—C7	1.207 (4)	C8—C9	1.439 (6)
O4—C7	1.319 (4)	C8—H8A	0.9700
O4—C8	1.463 (4)	C8—H8B	0.9700
O5—C10	1.213 (3)	C9—H9A	0.9600
O6—C10	1.329 (4)	C9—H9B	0.9600
O6—C11	1.451 (3)	C9—H9C	0.9600
C1—C2	1.373 (4)	C11—C12	1.483 (5)
C1—C7	1.468 (4)	C11—H11A	0.9700
C2—C3	1.425 (4)	C11—H11B	0.9700
C3—C4	1.376 (4)	C12—H12A	0.9600
C4—C10	1.463 (4)	C12—H12B	0.9600
C5A—C6A	1.48 (3)	C12—H12C	0.9600
C5A—H5A1	0.9700

C4—S1—C1	91.98 (13)	H5B1—C5B—H5B2	108.2
C2—O1—C5B	111.5 (4)	O2—C6B—C5B	110.0 (11)
C2—O1—C5A	111.2 (6)	O2—C6B—H6B1	109.7
C5B—O1—C5A	33.1 (6)	C5B—C6B—H6B1	109.7
C3—O2—C6B	112.4 (4)	O2—C6B—H6B2	109.7
C3—O2—C6A	111.3 (7)	C5B—C6B—H6B2	109.7
C6B—O2—C6A	28.4 (6)	H6B1—C6B—H6B2	108.2
C7—O4—C8	117.3 (3)	O3—C7—O4	125.4 (3)
C10—O6—C11	115.5 (2)	O3—C7—C1	121.2 (3)
C2—C1—C7	131.7 (3)	O4—C7—C1	113.4 (3)
C2—C1—S1	111.6 (2)	C9—C8—O4	110.4 (3)
C7—C1—S1	116.7 (2)	C9—C8—H8A	109.6
O1—C2—C1	125.0 (3)	O4—C8—H8A	109.6
O1—C2—C3	122.6 (2)	C9—C8—H8B	109.6
C1—C2—C3	112.4 (2)	O4—C8—H8B	109.6
O2—C3—C4	124.8 (2)	H8A—C8—H8B	108.1
O2—C3—C2	122.8 (2)	C8—C9—H9A	109.5
C4—C3—C2	112.4 (2)	C8—C9—H9B	109.5
C3—C4—C10	131.5 (3)	H9A—C9—H9B	109.5
C3—C4—S1	111.6 (2)	C8—C9—H9C	109.5
C10—C4—S1	116.8 (2)	H9A—C9—H9C	109.5
O1—C5A—C6A	108.4 (18)	H9B—C9—H9C	109.5
O1—C5A—H5A1	110.0	O5—C10—O6	124.2 (3)
C6A—C5A—H5A1	110.0	O5—C10—C4	122.8 (3)
O1—C5A—H5A2	110.0	O6—C10—C4	112.9 (2)
C6A—C5A—H5A2	110.0	O6—C11—C12	107.9 (3)
H5A1—C5A—H5A2	108.4	O6—C11—H11A	110.1
O2—C6A—C5A	110.1 (18)	C12—C11—H11A	110.1
O2—C6A—H6A1	109.6	O6—C11—H11B	110.1
C5A—C6A—H6A1	109.6	C12—C11—H11B	110.1
O2—C6A—H6A2	109.6	H11A—C11—H11B	108.4
C5A—C6A—H6A2	109.6	C11—C12—H12A	109.5
H6A1—C6A—H6A2	108.2	C11—C12—H12B	109.5
O1—C5B—C6B	109.7 (11)	H12A—C12—H12B	109.5
O1—C5B—H5B1	109.7	C11—C12—H12C	109.5
C6B—C5B—H5B1	109.7	H12A—C12—H12C	109.5
O1—C5B—H5B2	109.7	H12B—C12—H12C	109.5
C6B—C5B—H5B2	109.7

C4—S1—C1—C2	−0.5 (2)	C2—O1—C5A—C6A	−50 (3)
C4—S1—C1—C7	−179.3 (2)	C5B—O1—C5A—C6A	46.7 (17)
C5B—O1—C2—C1	162.8 (8)	C3—O2—C6A—C5A	−48 (2)
C5A—O1—C2—C1	−161.5 (13)	C6B—O2—C6A—C5A	50 (2)
C5B—O1—C2—C3	−16.3 (9)	O1—C5A—C6A—O2	67 (3)
C5A—O1—C2—C3	19.4 (13)	C2—O1—C5B—C6B	47.5 (16)
C7—C1—C2—O1	−0.2 (5)	C5A—O1—C5B—C6B	−48.7 (13)
S1—C1—C2—O1	−178.7 (2)	C3—O2—C6B—C5B	46.3 (17)
C7—C1—C2—C3	179.0 (3)	C6A—O2—C6B—C5B	−47.3 (18)
S1—C1—C2—C3	0.5 (3)	O1—C5B—C6B—O2	−65 (2)
C6B—O2—C3—C4	164.7 (8)	C8—O4—C7—O3	1.9 (5)
C6A—O2—C3—C4	−164.7 (11)	C8—O4—C7—C1	−178.7 (3)
C6B—O2—C3—C2	−14.9 (9)	C2—C1—C7—O3	−174.9 (3)
C6A—O2—C3—C2	15.7 (11)	S1—C1—C7—O3	3.5 (4)
O1—C2—C3—O2	−1.3 (4)	C2—C1—C7—O4	5.7 (5)
C1—C2—C3—O2	179.5 (2)	S1—C1—C7—O4	−175.8 (2)
O1—C2—C3—C4	179.0 (3)	C7—O4—C8—C9	95.4 (4)
C1—C2—C3—C4	−0.2 (4)	C11—O6—C10—O5	−1.4 (4)
O2—C3—C4—C10	−1.2 (5)	C11—O6—C10—C4	−179.1 (2)
C2—C3—C4—C10	178.4 (3)	C3—C4—C10—O5	−175.0 (3)
O2—C3—C4—S1	−179.9 (2)	S1—C4—C10—O5	3.6 (4)
C2—C3—C4—S1	−0.2 (3)	C3—C4—C10—O6	2.7 (5)
C1—S1—C4—C3	0.4 (2)	S1—C4—C10—O6	−178.76 (18)
C1—S1—C4—C10	−178.4 (2)	C10—O6—C11—C12	−178.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O3ⁱ	0.96	2.66	3.333 (5)	127
C9—H9A···O3ⁱⁱ	0.96	2.62	3.523 (7)	157
C6B—H6B1···O5ⁱⁱⁱ	0.97	2.68	3.233 (12)	117

Symmetry codes: (i) −x+3, −y, −z; (ii) −x+2, −y, −z; (iii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄O₆S
M_r	286.30
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	4.6805 (8), 8.3673 (17), 17.351 (3)
α, β, γ (°)	94.294 (7), 92.024 (9), 105.641 (9)
V (Å³)	651.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.60 × 0.10 × 0.08

Data collection
Diffractometer	Rigaku/MSC Mercury CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5181, 2899, 2300
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.069, 0.176, 1.11
No. of reflections	2899
No. of parameters	193
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.26

Computer programs: CrystalClear (Rigaku/MSC, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003) and Mercury (Macrae et al., 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···O3ⁱ	0.96	2.66	3.333 (5)	127.1
C9—H9A···O3ⁱⁱ	0.96	2.62	3.523 (7)	157.1
C6B—H6B1···O5ⁱⁱⁱ	0.97	2.68	3.233 (12)	116.5

Symmetry codes: (i) −x+3, −y, −z; (ii) −x+2, −y, −z; (iii) x+1, y+1, z.

Acknowledgements

This work was supported by a Grant-in-Aid (grant No. 19550034) from the Ministry of Education, Culture, Sports, Science and Technology, Japan. The authors thank the Instrument Center of the Institute for Molecular Science for the X-ray structure analysis.

References

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