Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015379/dn6004sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015379/dn6004Isup2.hkl |
CCDC reference: 175373
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.006 Å
- R factor = 0.084
- wR factor = 0.268
- Data-to-parameter ratio = 16.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level B:
DIFMX_01 Alert B The maximum difference density is > 0.1*ZMAX*1.00 _refine_diff_density_max given = 1.728 Test value = 1.600 PLAT_030 Alert B Refined Extinction parameter within range .... 2.22 Sigma
Alert Level C:
DIFMX_02 Alert C The minimum difference density is > 0.1*ZMAX*0.75 The relevant atom site should be identified. RFACR_01 Alert C The value of the weighted R factor is > 0.25 Weighted R factor given 0.268
0 Alert Level A = Potentially serious problem
2 Alert Level B = Potential problem
2 Alert Level C = Please check
2-Ethyl 5-methyl 3-hydroxythiophene-2,5-dicarboxylate, (I), was formed from the reaction of ethyl thioglycolate, (II), with dimethylacetylene dicarboxylate (DMAD) in the presence of DBU. The reaction proceeds via a Michael addition of (II) to DMAD, followed by an in situ Dieckmann cyclization. This reaction was originally observed in an attempted non-classical Wittig reaction of (II) with DMAD and PPh3 (Evans et al., 2001).
The quality of the crystal was poor, showing crazed faces, which produced a diffraction pattern with split reflections. The integration of the reflections was performed with a large box size and small spot size, in order to attempt to measure only one component of the splitting, however,in such a bad case, some intensities will inevitably be enhanced or reduced. This severely affected the refinement and final structure as demonstrated by the statistics of fit, residual density, etc. H atoms were included in idealized positions with coordinates and displacement parameters allowed to ride on those of the parent atom.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1993).
C9H10O5S | Z = 4 |
Mr = 230.23 | F(000) = 480 |
Triclinic, P1 | Dx = 1.478 Mg m−3 |
a = 7.6602 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.120 (2) Å | Cell parameters from 9463 reflections |
c = 12.572 (3) Å | θ = 2.9–27.5° |
α = 94.09 (3)° | µ = 0.31 mm−1 |
β = 102.64 (3)° | T = 120 K |
γ = 95.77 (3)° | Block, colourless |
V = 1034.8 (4) Å3 | 0.2 × 0.18 × 0.06 mm |
Nonius KappaCCD area-detector diffractometer | 4585 independent reflections |
Radiation source: Nonius FR591 rotating anode | 3689 reflections with I > 2σ(I) |
Detector resolution: 9.091 pixels mm-1 | Rint = 0.067 |
ϕ and ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −9→9 |
Tmin = 0.940, Tmax = 0.982 | k = −14→14 |
11567 measured reflections | l = −16→15 |
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.1293P)2 + 5.7167P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.085 | (Δ/σ)max = 0.02 |
wR(F2) = 0.268 | Δρmax = 1.73 e Å−3 |
S = 1.05 | Δρmin = −0.70 e Å−3 |
4585 reflections | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
277 parameters | Extinction coefficient: 0.020 (9) |
0 restraints |
C9H10O5S | γ = 95.77 (3)° |
Mr = 230.23 | V = 1034.8 (4) Å3 |
Triclinic, P1 | Z = 4 |
a = 7.6602 (15) Å | Mo Kα radiation |
b = 11.120 (2) Å | µ = 0.31 mm−1 |
c = 12.572 (3) Å | T = 120 K |
α = 94.09 (3)° | 0.2 × 0.18 × 0.06 mm |
β = 102.64 (3)° |
Nonius KappaCCD area-detector diffractometer | 4585 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 3689 reflections with I > 2σ(I) |
Tmin = 0.940, Tmax = 0.982 | Rint = 0.067 |
11567 measured reflections |
R[F2 > 2σ(F2)] = 0.085 | 0 restraints |
wR(F2) = 0.268 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.73 e Å−3 |
4585 reflections | Δρmin = −0.70 e Å−3 |
277 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1020 (6) | 0.8616 (4) | 0.1125 (3) | 0.0173 (9) | |
C2 | 0.0445 (6) | 0.7823 (4) | 0.0168 (3) | 0.0182 (9) | |
C3 | −0.0531 (6) | 0.6743 (4) | 0.0314 (3) | 0.0179 (9) | |
H3 | −0.1037 | 0.6112 | −0.0252 | 0.021* | |
C4 | −0.0665 (6) | 0.6711 (4) | 0.1389 (3) | 0.0173 (9) | |
C5 | 0.2018 (6) | 0.9802 (4) | 0.1200 (4) | 0.0196 (9) | |
C6 | 0.3425 (7) | 1.1587 (4) | 0.2326 (4) | 0.0250 (10) | |
H6A | 0.2659 | 1.2176 | 0.1966 | 0.03* | |
H6B | 0.4478 | 1.1559 | 0.1992 | 0.03* | |
C7 | 0.4038 (7) | 1.1955 (5) | 0.3553 (4) | 0.0288 (11) | |
H7A | 0.2982 | 1.2009 | 0.3866 | 0.043* | |
H7B | 0.4778 | 1.2746 | 0.368 | 0.043* | |
H7C | 0.475 | 1.1345 | 0.3901 | 0.043* | |
C8 | −0.1540 (6) | 0.5754 (4) | 0.1913 (4) | 0.0213 (9) | |
C9 | −0.3363 (9) | 0.3880 (5) | 0.1654 (5) | 0.0362 (13) | |
H9A | −0.2455 | 0.3496 | 0.2148 | 0.054* | |
H9B | −0.405 | 0.3274 | 0.1069 | 0.054* | |
H9C | −0.4182 | 0.4213 | 0.2065 | 0.054* | |
C10 | 0.4102 (6) | 1.1500 (4) | −0.2462 (3) | 0.0177 (9) | |
C11 | 0.4792 (6) | 1.2216 (4) | −0.1474 (4) | 0.0200 (9) | |
C12 | 0.5760 (6) | 1.3324 (4) | −0.1600 (4) | 0.0189 (9) | |
H12 | 0.6314 | 1.3925 | −0.1015 | 0.023* | |
C13 | 0.5797 (6) | 1.3420 (4) | −0.2679 (4) | 0.0193 (9) | |
C14 | 0.3042 (6) | 1.0322 (4) | −0.2554 (4) | 0.0184 (9) | |
C15 | 0.1275 (7) | 0.8674 (5) | −0.3723 (4) | 0.0281 (11) | |
H15A | 0.0185 | 0.8762 | −0.3436 | 0.034* | |
H15B | 0.1958 | 0.8078 | −0.3312 | 0.034* | |
C16 | 0.0748 (7) | 0.8243 (5) | −0.4930 (4) | 0.0268 (10) | |
H16A | 0.0043 | 0.8827 | −0.5327 | 0.04* | |
H16B | 0.0022 | 0.7448 | −0.5038 | 0.04* | |
H16C | 0.1836 | 0.8174 | −0.5209 | 0.04* | |
C17 | 0.6773 (6) | 1.4418 (4) | −0.3094 (4) | 0.0205 (9) | |
C18 | 0.7694 (7) | 1.5099 (5) | −0.4642 (4) | 0.0287 (11) | |
H18A | 0.7183 | 1.587 | −0.4598 | 0.043* | |
H18B | 0.7622 | 1.4826 | −0.541 | 0.043* | |
H18C | 0.8958 | 1.5214 | −0.424 | 0.043* | |
O1 | 0.2456 (5) | 1.0210 (3) | 0.0414 (3) | 0.0259 (8) | |
O2 | 0.2403 (5) | 1.0387 (3) | 0.2207 (3) | 0.0232 (7) | |
O3 | 0.0755 (5) | 0.8058 (3) | −0.0820 (2) | 0.0217 (7) | |
H3A | 0.1326 | 0.8753 | −0.0769 | 0.033* | |
O4 | −0.1432 (5) | 0.5783 (3) | 0.2892 (3) | 0.0247 (7) | |
O5 | −0.2478 (5) | 0.4852 (3) | 0.1179 (3) | 0.0247 (7) | |
O6 | 0.2804 (5) | 0.9828 (3) | −0.1758 (3) | 0.0266 (8) | |
O7 | 0.2387 (4) | 0.9840 (3) | −0.3593 (2) | 0.0212 (7) | |
O8 | 0.4581 (5) | 1.1940 (3) | −0.0480 (3) | 0.0249 (7) | |
H8 | 0.3961 | 1.126 | −0.0541 | 0.037* | |
O9 | 0.7556 (5) | 1.5338 (3) | −0.2526 (3) | 0.0296 (8) | |
O10 | 0.6700 (5) | 1.4204 (3) | −0.4169 (3) | 0.0247 (7) | |
S1 | 0.03654 (14) | 0.79934 (10) | 0.22139 (8) | 0.0179 (3) | |
S2 | 0.46669 (15) | 1.21826 (10) | −0.35415 (9) | 0.0192 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.022 (2) | 0.018 (2) | 0.0128 (19) | 0.0020 (16) | 0.0061 (16) | 0.0016 (16) |
C2 | 0.020 (2) | 0.022 (2) | 0.0127 (19) | 0.0031 (17) | 0.0043 (16) | 0.0024 (16) |
C3 | 0.016 (2) | 0.022 (2) | 0.015 (2) | 0.0003 (16) | 0.0030 (15) | 0.0030 (16) |
C4 | 0.017 (2) | 0.021 (2) | 0.0162 (19) | 0.0035 (16) | 0.0058 (15) | 0.0067 (16) |
C5 | 0.022 (2) | 0.024 (2) | 0.015 (2) | 0.0050 (17) | 0.0082 (17) | 0.0019 (17) |
C6 | 0.030 (2) | 0.020 (2) | 0.023 (2) | −0.0005 (18) | 0.0021 (19) | 0.0019 (18) |
C7 | 0.031 (3) | 0.035 (3) | 0.023 (2) | 0.009 (2) | 0.011 (2) | −0.001 (2) |
C8 | 0.019 (2) | 0.022 (2) | 0.022 (2) | −0.0014 (17) | 0.0055 (17) | 0.0014 (18) |
C9 | 0.057 (4) | 0.022 (3) | 0.033 (3) | −0.010 (2) | 0.025 (3) | 0.002 (2) |
C10 | 0.021 (2) | 0.020 (2) | 0.0140 (19) | 0.0025 (17) | 0.0061 (16) | 0.0045 (16) |
C11 | 0.021 (2) | 0.024 (2) | 0.016 (2) | 0.0057 (17) | 0.0045 (16) | 0.0065 (17) |
C12 | 0.018 (2) | 0.019 (2) | 0.020 (2) | 0.0020 (16) | 0.0051 (16) | 0.0013 (17) |
C13 | 0.020 (2) | 0.017 (2) | 0.022 (2) | 0.0028 (16) | 0.0062 (17) | 0.0008 (17) |
C14 | 0.016 (2) | 0.023 (2) | 0.016 (2) | −0.0001 (16) | 0.0059 (16) | 0.0004 (17) |
C15 | 0.034 (3) | 0.025 (2) | 0.023 (2) | −0.010 (2) | 0.007 (2) | 0.0014 (19) |
C16 | 0.030 (3) | 0.032 (3) | 0.016 (2) | 0.004 (2) | −0.0002 (18) | −0.0015 (19) |
C17 | 0.018 (2) | 0.023 (2) | 0.022 (2) | 0.0042 (17) | 0.0081 (17) | 0.0046 (18) |
C18 | 0.031 (3) | 0.028 (3) | 0.031 (3) | 0.002 (2) | 0.014 (2) | 0.008 (2) |
O1 | 0.0350 (19) | 0.0261 (18) | 0.0184 (16) | −0.0022 (14) | 0.0125 (14) | 0.0022 (13) |
O2 | 0.0281 (17) | 0.0228 (17) | 0.0187 (16) | 0.0003 (13) | 0.0065 (13) | 0.0018 (13) |
O3 | 0.0272 (17) | 0.0230 (17) | 0.0144 (15) | −0.0027 (13) | 0.0056 (12) | 0.0026 (12) |
O4 | 0.0312 (18) | 0.0253 (18) | 0.0187 (16) | −0.0008 (14) | 0.0088 (13) | 0.0051 (13) |
O5 | 0.0353 (19) | 0.0210 (17) | 0.0183 (16) | −0.0067 (14) | 0.0127 (14) | −0.0007 (13) |
O6 | 0.0335 (19) | 0.0273 (18) | 0.0181 (16) | −0.0041 (14) | 0.0079 (14) | 0.0012 (14) |
O7 | 0.0227 (16) | 0.0242 (17) | 0.0152 (15) | −0.0031 (13) | 0.0034 (12) | 0.0026 (12) |
O8 | 0.0329 (18) | 0.0270 (18) | 0.0144 (15) | −0.0048 (14) | 0.0082 (13) | 0.0025 (13) |
O9 | 0.035 (2) | 0.0220 (18) | 0.0336 (19) | −0.0047 (14) | 0.0157 (16) | −0.0015 (15) |
O10 | 0.0290 (18) | 0.0246 (17) | 0.0218 (16) | −0.0026 (13) | 0.0100 (14) | 0.0062 (13) |
S1 | 0.0195 (6) | 0.0206 (6) | 0.0142 (5) | 0.0018 (4) | 0.0055 (4) | 0.0017 (4) |
S2 | 0.0202 (6) | 0.0225 (6) | 0.0151 (5) | −0.0009 (4) | 0.0056 (4) | 0.0032 (4) |
C1—C2 | 1.399 (6) | C10—C14 | 1.453 (6) |
C1—C5 | 1.442 (6) | C10—S2 | 1.716 (4) |
C1—S1 | 1.724 (4) | C11—O8 | 1.348 (5) |
C2—O3 | 1.353 (5) | C11—C12 | 1.410 (6) |
C2—C3 | 1.395 (6) | C12—C13 | 1.375 (6) |
C3—C4 | 1.380 (6) | C12—H12 | 0.95 |
C3—H3 | 0.95 | C13—C17 | 1.466 (6) |
C4—C8 | 1.471 (6) | C13—S2 | 1.719 (5) |
C4—S1 | 1.714 (5) | C14—O6 | 1.214 (6) |
C5—O1 | 1.213 (6) | C14—O7 | 1.343 (5) |
C5—O2 | 1.339 (5) | C15—O7 | 1.456 (6) |
C6—O2 | 1.459 (6) | C15—C16 | 1.512 (6) |
C6—C7 | 1.523 (7) | C15—H15A | 0.99 |
C6—H6A | 0.99 | C15—H15B | 0.99 |
C6—H6B | 0.99 | C16—H16A | 0.98 |
C7—H7A | 0.98 | C16—H16B | 0.98 |
C7—H7B | 0.98 | C16—H16C | 0.98 |
C7—H7C | 0.98 | C17—O9 | 1.225 (6) |
C8—O4 | 1.214 (6) | C17—O10 | 1.343 (6) |
C8—O5 | 1.344 (6) | C18—O10 | 1.433 (6) |
C9—O5 | 1.451 (6) | C18—H18A | 0.98 |
C9—H9A | 0.98 | C18—H18B | 0.98 |
C9—H9B | 0.98 | C18—H18C | 0.98 |
C9—H9C | 0.98 | O3—H3A | 0.84 |
C10—C11 | 1.394 (6) | O8—H8 | 0.84 |
C2—C1—C5 | 125.0 (4) | O8—C11—C12 | 120.8 (4) |
C2—C1—S1 | 111.0 (3) | C10—C11—C12 | 113.0 (4) |
C5—C1—S1 | 124.0 (3) | C13—C12—C11 | 111.1 (4) |
O3—C2—C3 | 121.8 (4) | C13—C12—H12 | 124.5 |
O3—C2—C1 | 124.7 (4) | C11—C12—H12 | 124.5 |
C3—C2—C1 | 113.5 (4) | C12—C13—C17 | 125.6 (4) |
C4—C3—C2 | 111.1 (4) | C12—C13—S2 | 113.4 (3) |
C4—C3—H3 | 124.4 | C17—C13—S2 | 120.9 (3) |
C2—C3—H3 | 124.4 | O6—C14—O7 | 124.1 (4) |
C3—C4—C8 | 129.8 (4) | O6—C14—C10 | 122.4 (4) |
C3—C4—S1 | 113.5 (3) | O7—C14—C10 | 113.6 (4) |
C8—C4—S1 | 116.7 (3) | O7—C15—C16 | 107.9 (4) |
O1—C5—O2 | 124.3 (4) | O7—C15—H15A | 110.1 |
O1—C5—C1 | 122.1 (4) | C16—C15—H15A | 110.1 |
O2—C5—C1 | 113.6 (4) | O7—C15—H15B | 110.1 |
O2—C6—C7 | 106.2 (4) | C16—C15—H15B | 110.1 |
O2—C6—H6A | 110.5 | H15A—C15—H15B | 108.4 |
C7—C6—H6A | 110.5 | C15—C16—H16A | 109.5 |
O2—C6—H6B | 110.5 | C15—C16—H16B | 109.5 |
C7—C6—H6B | 110.5 | H16A—C16—H16B | 109.5 |
H6A—C6—H6B | 108.7 | C15—C16—H16C | 109.5 |
C6—C7—H7A | 109.5 | H16A—C16—H16C | 109.5 |
C6—C7—H7B | 109.5 | H16B—C16—H16C | 109.5 |
H7A—C7—H7B | 109.5 | O9—C17—O10 | 124.2 (4) |
C6—C7—H7C | 109.5 | O9—C17—C13 | 123.9 (4) |
H7A—C7—H7C | 109.5 | O10—C17—C13 | 111.9 (4) |
H7B—C7—H7C | 109.5 | O10—C18—H18A | 109.5 |
O4—C8—O5 | 124.1 (4) | O10—C18—H18B | 109.5 |
O4—C8—C4 | 123.8 (4) | H18A—C18—H18B | 109.5 |
O5—C8—C4 | 112.1 (4) | O10—C18—H18C | 109.5 |
O5—C9—H9A | 109.5 | H18A—C18—H18C | 109.5 |
O5—C9—H9B | 109.5 | H18B—C18—H18C | 109.5 |
H9A—C9—H9B | 109.5 | C5—O2—C6 | 115.6 (4) |
O5—C9—H9C | 109.5 | C2—O3—H3A | 109.5 |
H9A—C9—H9C | 109.5 | C8—O5—C9 | 114.3 (4) |
H9B—C9—H9C | 109.5 | C14—O7—C15 | 115.3 (3) |
C11—C10—C14 | 123.7 (4) | C11—O8—H8 | 109.5 |
C11—C10—S2 | 111.6 (3) | C17—O10—C18 | 116.2 (4) |
C14—C10—S2 | 124.7 (3) | C4—S1—C1 | 90.9 (2) |
O8—C11—C10 | 126.1 (4) | C10—S2—C13 | 91.0 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O1 | 0.84 | 2.1 | 2.791 (5) | 140 |
O3—H3A···O6 | 0.84 | 2.19 | 2.873 (5) | 138 |
O8—H8···O1 | 0.84 | 2.16 | 2.845 (5) | 138 |
O8—H8···O6 | 0.84 | 2.11 | 2.795 (5) | 139 |
Experimental details
Crystal data | |
Chemical formula | C9H10O5S |
Mr | 230.23 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 7.6602 (15), 11.120 (2), 12.572 (3) |
α, β, γ (°) | 94.09 (3), 102.64 (3), 95.77 (3) |
V (Å3) | 1034.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.2 × 0.18 × 0.06 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.940, 0.982 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11567, 4585, 3689 |
Rint | 0.067 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.085, 0.268, 1.05 |
No. of reflections | 4585 |
No. of parameters | 277 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.73, −0.70 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1993).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O1 | 0.84 | 2.1 | 2.791 (5) | 139.7 |
O3—H3A···O6 | 0.84 | 2.19 | 2.873 (5) | 137.8 |
O8—H8···O1 | 0.84 | 2.16 | 2.845 (5) | 138.3 |
O8—H8···O6 | 0.84 | 2.11 | 2.795 (5) | 138.9 |
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The title compound, (I), crystallizes with two chemically equivalent but crystallographically independent molecules in the asymmetric unit and is shown, along with the atom numbering scheme, in Fig. 1.
The structure is composed of a thiophene ring substituted in the 2-position by an ethyl ester, in the 3-position by a hydroxyl group and in the 5- position by a methyl ester. This arrangement produces a virtually planar molecule with only the methyl and ethyl H atoms deviating from the plane. Maximum deviations from the heavy-atom plane are 0.124 (C7) and 0.195 Å (O6) for molecules A and B, respectively. All bond lengths and angles fall into accepted ranges reported from an assessment of the Cambridge Structural Database (Allen & Kennard, 1993; Orpen et al., 1992). Pertinent non-bonded interactions are detailed in Table 1. Intramolecular hydrogen bonds exist in molecule a between O3—H3A···O1 and concordantly between O8—H8···O6 in molecule B. These intramolecular interactions are bifurcated, as strong intermolecular hydrogen bonds between O3—H3A···O6 and O8—H8···O1 allow dimeric association of the two independent molecules. These dimer units produce a crystal structure composed of sheets, stacked parallel to the c axis.