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

Volume 64
Part 2
Page o468
February 2008

Received 22 December 2007
Accepted 10 January 2008
Online 18 January 2008

Key indicators
Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.004 Å
Disorder in main residue
R = 0.070
wR = 0.177
Data-to-parameter ratio = 15.0
Details

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

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-HO 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
= 94.294 (7)°
= 92.024 (9)°
= 105.641 (9)°
V = 651.4 (2) Å³
Z = 2
Mo K radiation
= 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 > 2(I)
R_int = 0.036

Refinement

R[F² > 2(F²)] = 0.069
wR(F²) = 0.176
S = 1.11
2899 reflections
193 parameters
H-atom parameters constrained
_max = 0.55 e Å^-3
_min = -0.26 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
C9-H9BO3ⁱ	0.96	2.66	3.333 (5)	127
C9-H9AO3ⁱⁱ	0.96	2.62	3.523 (7)	157
C6B-H6B1O5ⁱⁱⁱ	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.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2368 ).

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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Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.
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Caras-Quintero, D. & Bäuerle, P. (2002). Chem. Commun. pp. 2690-2691.
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Rigaku/MSC (2001). CrystalClear. Version 1.3. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
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Zong, K., Madrigal, L., Groenendaal, L. & Reynolds, J. R. (2002). Chem. Commun. pp. 2498-2499.

organic compounds