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access2-Oxo-2-(2-thienyl)acetic acid
aDepartment of Chemistry and Biochemistry, Central Connecticut State University, 1619 Stanley Street, New Britain, CT 06053, USA
*Correspondence e-mail: crundwellg@ccsu.edu
The structure of the title compound, C6H4O3S, displays intermolecular hydrogen-bonding dimers. The structure exhibits a thienyl-ring flip disorder of the main molecule [occupancy ratio = 91.3 (2):8.7 (2)].
Related literature
For a discussion of ring-flip disorder in unsubstituted 2- and 3-thienyl rings, see: Crundwell et al. (2003![[Crundwell, G., Sullivan, J., Pelto, R. & Kantardjieff, K. (2003). J. Chem. Crystallogr. 33, 239-244.]](../../../../../../logos/arrows/e_arr.gif "Crundwell, G., Sullivan, J., Pelto, R. & Kantardjieff, K. (2003). J. Chem. Crystallogr. 33, 239-244.")
). For information on simple O—H⋯O interactions, see: Bernstein et al. (1995).
![[Scheme 1]](bx2317scheme1.gif)
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681004403X/bx2317sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681004403X/bx2317Isup2.hkl
The title compound was purchased as 2-thiopheneglyoxylic acid from Aldrich (95% purity). Crystals for this x-ray diffraction study were harvested from methanol during routine recrystallization.
During the thienyl ring showed evidence of ring-flip disorder which is common for unsubstituted 2- and 3-thienyl rings (Crundwell et al., 2003). After finding three of the flipped disordered atoms in the difference map, the rest of the ring was generated and modeled. The final model suggested that the thienyl ring disorder was 8.7 (2)%.
Hydrogen atoms on carbons were included in calculated positions with a C—H distance of 0.93 Å and were included in the in riding motion approximation with Uiso = 1.2Ueq of the carrier atom.
The hydroxyl hydrogen was included in a calculated position with a O—H distance of 0.82 Å and was included in the in riding motion approximation with Uiso = 1.2Ueq of the carrier atom.
The structure of 2-oxo-2-(2-thienyl)acetic acid, C6H4O3S, has monoclinic (P21/c) symmetry. The structure displays intermolecular hydrogen bonding dimers. The structure exhibits a thienyl-ring flip disorder of the main molecule.
The structure of the title compound displays centrosymmetric R22(8) dimers by a simple O—H···O interactions (Bernstein et al., 1995). The structure exhibits a thienyl-ring flip disorder of the main molecule with occupancy ratios of 91.3 (2)% to 8.7 (2)%.
For a discussion of ring-flip disorder in unsubstituted 2- and 3-thienyl rings, see: Crundwell et al. (2003). For related literature [please provide some indication of what these references refer to], Steel & Fitchett (2000, 2006).
For related literature, see: Spek (2009).
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bx2317fig1thm.gif) | Fig. 1. A view of the title compound (Farrugia, 1997). Displacement ellipsoids are drawn at the 50% probability level. |
| C6H4O3S | F(000) = 320 |
| Mr = 156.15 | Dx = 1.687 Mg m−3 |
| Monoclinic, P21/c | Melting point: 361 K |
| Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
| a = 3.7481 (10) Å | Cell parameters from 6632 reflections |
| b = 15.314 (3) Å | θ = 3.8–32.0° |
| c = 10.727 (3) Å | µ = 0.46 mm−1 |
| β = 93.30 (2)° | T = 293 K |
| V = 614.7 (3) Å3 | Plate, yellow |
| Z = 4 | 0.34 × 0.21 × 0.11 mm |
| Oxford Diffraction Xcalibur Sapphire3 diffractometer | 1927 independent reflections |
| Radiation source: Enhance (Mo) X-ray Source | 1512 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.032 |
| Detector resolution: 16.1790 pixels mm-1 | θmax = 32.0°, θmin = 3.8° |
| ω scans | h = −5→5 |
| Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | k = −22→16 |
| Tmin = 0.944, Tmax = 1.000 | l = −15→15 |
| 6475 measured reflections |
| 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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.106 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0678P)2 + 0.018P] where P = (Fo2 + 2Fc2)/3 |
| 1927 reflections | (Δ/σ)max = 0.002 |
| 104 parameters | Δρmax = 0.51 e Å−3 |
| 12 restraints | Δρmin = −0.29 e Å−3 |
| C6H4O3S | V = 614.7 (3) Å3 |
| Mr = 156.15 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 3.7481 (10) Å | µ = 0.46 mm−1 |
| b = 15.314 (3) Å | T = 293 K |
| c = 10.727 (3) Å | 0.34 × 0.21 × 0.11 mm |
| β = 93.30 (2)° |
| Oxford Diffraction Xcalibur Sapphire3 diffractometer | 1927 independent reflections |
| Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | 1512 reflections with I > 2σ(I) |
| Tmin = 0.944, Tmax = 1.000 | Rint = 0.032 |
| 6475 measured reflections |
| R[F2 > 2σ(F2)] = 0.037 | 12 restraints |
| wR(F2) = 0.106 | H-atom parameters constrained |
| S = 1.09 | Δρmax = 0.51 e Å−3 |
| 1927 reflections | Δρmin = −0.29 e Å−3 |
| 104 parameters |
Experimental. Hydrogen atoms on carbons were included in calculated positions with a C—H distance of 0.93 Å and were included in the refinement in riding motion approximation with Uiso = 1.2Ueq of the carrier atom. The hydroxyl hydrogen was included in a calculated position with a O—H distance of 0.82 Å and was included in the refinement in riding motion approximation with Uiso = 1.2Ueq of the carrier atom. |
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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| O1 | 0.1858 (3) | 0.98317 (6) | 0.36658 (10) | 0.0261 (3) | |
| H1 | 0.2759 | 1.0208 | 0.4128 | 0.039* | |
| O2 | 0.5095 (3) | 0.89316 (7) | 0.49326 (9) | 0.0207 (2) | |
| C1 | 0.2916 (4) | 0.90590 (8) | 0.40596 (12) | 0.0167 (3) | |
| C2 | 0.1123 (4) | 0.83170 (8) | 0.32857 (12) | 0.0156 (3) | |
| O3 | −0.0839 (3) | 0.85113 (7) | 0.23733 (9) | 0.0207 (2) | |
| C3 | 0.1813 (3) | 0.74199 (8) | 0.36784 (12) | 0.0153 (3) | 0.9131 (17) |
| C4 | 0.3362 (8) | 0.70703 (19) | 0.4767 (2) | 0.0176 (4) | 0.9131 (17) |
| H4 | 0.4368 | 0.7412 | 0.5413 | 0.021* | 0.9131 (17) |
| C5 | 0.3282 (10) | 0.61491 (14) | 0.4812 (2) | 0.0158 (3) | 0.9131 (17) |
| H5 | 0.4176 | 0.5815 | 0.5484 | 0.019* | 0.9131 (17) |
| C6 | 0.1687 (5) | 0.58091 (10) | 0.37166 (15) | 0.0158 (3) | 0.9131 (17) |
| H6 | 0.1417 | 0.5214 | 0.3564 | 0.019* | 0.9131 (17) |
| S1 | 0.02766 (10) | 0.65987 (2) | 0.26826 (3) | 0.01633 (14) | 0.9131 (17) |
| C3B | 0.1813 (3) | 0.74199 (8) | 0.36784 (12) | 0.0153 (3) | 0.0869 (17) |
| C4B | 0.057 (4) | 0.6842 (10) | 0.2959 (14) | 0.01633 (14) | 0.0869 (17) |
| H4B | −0.0609 | 0.6947 | 0.2187 | 0.020* | 0.0869 (17) |
| C5B | 0.122 (6) | 0.5982 (11) | 0.350 (2) | 0.0158 (3) | 0.0869 (17) |
| H5B | 0.0539 | 0.5454 | 0.3127 | 0.019* | 0.0869 (17) |
| C6B | 0.303 (13) | 0.6081 (13) | 0.464 (3) | 0.0158 (3) | 0.0869 (17) |
| H6B | 0.3739 | 0.5612 | 0.5151 | 0.019* | 0.0869 (17) |
| S1B | 0.384 (3) | 0.7158 (6) | 0.5057 (7) | 0.0176 (4) | 0.0869 (17) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0349 (6) | 0.0124 (4) | 0.0291 (6) | 0.0006 (4) | −0.0140 (4) | −0.0003 (4) |
| O2 | 0.0264 (5) | 0.0153 (5) | 0.0193 (5) | 0.0004 (4) | −0.0080 (4) | −0.0003 (4) |
| C1 | 0.0180 (6) | 0.0151 (6) | 0.0170 (6) | −0.0003 (5) | 0.0004 (5) | −0.0007 (5) |
| C2 | 0.0166 (6) | 0.0150 (6) | 0.0152 (6) | 0.0009 (5) | −0.0005 (4) | −0.0003 (5) |
| O3 | 0.0245 (5) | 0.0203 (5) | 0.0166 (5) | 0.0016 (4) | −0.0060 (4) | 0.0009 (4) |
| C3 | 0.0159 (6) | 0.0132 (6) | 0.0165 (6) | 0.0006 (5) | −0.0005 (5) | −0.0015 (5) |
| C4 | 0.0204 (11) | 0.0172 (9) | 0.0147 (13) | −0.0002 (7) | −0.0017 (9) | −0.0020 (9) |
| C5 | 0.0181 (9) | 0.0144 (7) | 0.0147 (10) | 0.0001 (6) | −0.0009 (7) | −0.0009 (6) |
| C6 | 0.0160 (8) | 0.0128 (7) | 0.0184 (8) | 0.0012 (6) | −0.0017 (6) | 0.0023 (6) |
| S1 | 0.0178 (2) | 0.0142 (2) | 0.0167 (2) | −0.00080 (14) | −0.00148 (14) | −0.00162 (13) |
| C3B | 0.0159 (6) | 0.0132 (6) | 0.0165 (6) | 0.0006 (5) | −0.0005 (5) | −0.0015 (5) |
| C4B | 0.0178 (2) | 0.0142 (2) | 0.0167 (2) | −0.00080 (14) | −0.00148 (14) | −0.00162 (13) |
| C5B | 0.0160 (8) | 0.0128 (7) | 0.0184 (8) | 0.0012 (6) | −0.0017 (6) | 0.0023 (6) |
| C6B | 0.0181 (9) | 0.0144 (7) | 0.0147 (10) | 0.0001 (6) | −0.0009 (7) | −0.0009 (6) |
| S1B | 0.0204 (11) | 0.0172 (9) | 0.0147 (13) | −0.0002 (7) | −0.0017 (9) | −0.0020 (9) |
| O1—C1 | 1.3102 (16) | C5—C6 | 1.389 (2) |
| O1—H1 | 0.8200 | C5—H5 | 0.9300 |
| O2—C1 | 1.2223 (16) | C6—S1 | 1.7041 (15) |
| C1—C2 | 1.5387 (19) | C6—H6 | 0.9300 |
| C2—O3 | 1.2265 (17) | C4B—C5B | 1.452 (16) |
| C2—C3 | 1.4558 (18) | C4B—H4B | 0.9300 |
| C3—C4 | 1.382 (3) | C5B—C6B | 1.380 (17) |
| C3—S1 | 1.7272 (13) | C5B—H5B | 0.9300 |
| C4—C5 | 1.412 (3) | C6B—S1B | 1.730 (18) |
| C4—H4 | 0.9300 | C6B—H6B | 0.9300 |
| C1—O1—H1 | 109.5 | C6—C5—H5 | 124.6 |
| O2—C1—O1 | 124.58 (12) | C4—C5—H5 | 124.6 |
| O2—C1—C2 | 123.18 (12) | C5—C6—S1 | 112.77 (15) |
| O1—C1—C2 | 112.23 (11) | C5—C6—H6 | 123.6 |
| O3—C2—C3 | 123.25 (12) | S1—C6—H6 | 123.6 |
| O3—C2—C1 | 118.33 (12) | C6—S1—C3 | 91.96 (7) |
| C3—C2—C1 | 118.42 (11) | C5B—C4B—H4B | 124.7 |
| C4—C3—C2 | 132.00 (15) | C6B—C5B—C4B | 108.5 (16) |
| C4—C3—S1 | 110.46 (14) | C6B—C5B—H5B | 125.8 |
| C2—C3—S1 | 117.44 (10) | C4B—C5B—H5B | 125.8 |
| C3—C4—C5 | 114.04 (18) | C5B—C6B—S1B | 113.7 (16) |
| C3—C4—H4 | 123.0 | C5B—C6B—H6B | 123.1 |
| C5—C4—H4 | 123.0 | S1B—C6B—H6B | 123.1 |
| C6—C5—C4 | 110.76 (18) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2i | 0.82 | 1.82 | 2.637 (2) | 176 |
| Symmetry code: (i) −x+1, −y+2, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | C6H4O3S |
| Mr | 156.15 |
| Crystal system, space group | Monoclinic, P21/c |
| Temperature (K) | 293 |
| a, b, c (Å) | 3.7481 (10), 15.314 (3), 10.727 (3) |
| β (°) | 93.30 (2) |
| V (Å3) | 614.7 (3) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.46 |
| Crystal size (mm) | 0.34 × 0.21 × 0.11 |
| Data collection | |
| Diffractometer | Oxford Diffraction Xcalibur Sapphire3 |
| Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) |
| Tmin, Tmax | 0.944, 1.000 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6475, 1927, 1512 |
| Rint | 0.032 |
| (sin θ/λ)max (Å−1) | 0.746 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.106, 1.09 |
| No. of reflections | 1927 |
| No. of parameters | 104 |
| No. of restraints | 12 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.51, −0.29 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXTL (Sheldrick, 2008).
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O2i | 0.82 | 1.82 | 2.637 (2) | 176 |
| Symmetry code: (i) −x+1, −y+2, −z+1. |
Acknowledgements
This work was funded by a CSU-AAUP Faculty Research Grant.
References
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Crundwell, G., Sullivan, J., Pelto, R. & Kantardjieff, K. (2003). J. Chem. Crystallogr. 33, 239–244. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
The structure of 2-oxo-2-(2-thienyl)acetic acid, C6H4O3S, has monoclinic (P21/c) symmetry. The structure displays intermolecular hydrogen bonding dimers. The structure exhibits a thienyl-ring flip disorder of the main molecule.
The structure of the title compound displays centrosymmetric R22(8) dimers by a simple O—H···O interactions (Bernstein et al., 1995). The structure exhibits a thienyl-ring flip disorder of the main molecule with occupancy ratios of 91.3 (2)% to 8.7 (2)%.