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Ethyl 5-hydroxy-6-oxo-4-phenyl-5,6-dihydro-4H-cyclopenta[b]thiophene-5-carboxylate
aDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
*Correspondence e-mail: jsimpson@alkali.otago.ac.nz
In the title molecule, C16H14O4S, the dihydrocyclopentathiophenone ring system is almost planar, with an r.m.s. deviation of 0.060 Å from the best fit plane through all nine non-H atoms. The cyclopentanone ring adopts a severely flattened with the C atom carrying the OH and ethylcarboxylate substituents at the flap. This atom lies only 0.185 (3) Å from the plane through the other four C atoms. The phenyl substituent is inclined at 43.37 (5)° to the dihydrocyclopentathiophenone mean plane. In the crystal, molecules are linked by pairs of O—H⋯O hydrogen bonds, forming inversion dimers with R22(10) ring motifs. Weak C—H⋯O hydrogen bonds also link molecules into chains along c, while an approximately orthogonal set of C—H⋯O contacts form chains along b, resulting in layers lying parallel to (100). Inversion dimers also form through weaker R22(12) C—H⋯S contacts, which combine with C—H⋯O contacts to form stacks along b.
Related literature
For details of conducting thiophene polymers, see: Anquetil et al. (2003). For related structures, see: Bonini et al. (2004
); Chang et al. (2004
). For details of the Cambridge Structural Database, see: Allen (2002
). For hydrogen-bond motifs, see: Bernstein et al. (1995
). For standard bond lengths, see Allen et al. (1987
). For the preparation of a precursor used in the synthesis, see: Yang (2009
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2011); cell APEX2 and SAINT (Bruker, 2011
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
) and TITAN2000 (Hunter & Simpson, 1999
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
) and TITAN2000; molecular graphics: SHELXTL (Sheldrick, 2008
) and Mercury (Macrae et al., 2008
); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004
), PLATON (Spek, 2009
) and publCIF (Westrip 2010
).
Supporting information
https://doi.org/10.1107/S1600536811037032/su2314sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811037032/su2314Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811037032/su2314Isup3.cml
The precursor thiophene, ethyl 6-oxo-4-phenyl-5,6-dihydro-4H-cyclopenta- thiophene-5-carboxylate (EOPDCTC), was prepared by a literature procedure (Yang, 2009). EOPDCTC (315 mg, 1.1 mmol) and potassium tertiary butoxide (289 mg, 2.6 mmol) were dissolved in 2-propanol (5 ml) and iodine (280 mg, 1.1 mmol) in 2-propanol (5 ml) added dropwise under a N2 atmosphere. After stirring at room temperature for 24 hrs, the solvent was removed under reduced pressure. The residues were redissolved in EtOAc, washed with saturated sodium thiosulfate and distilled water then dried over MgSO4. The crude product was purified by silica gel
with CH2Cl2/EtOAc (10%) to give a brown solid in 17% yield. X-ray quality crystals were obtained from a CH2Cl2 solution of the title compound layered with hexane. M.p 404 K. HRMS (+ve ESI) m/z calc for C16H13O4SNa 324.0427, found 325.1152. Spectroscopic data for the title compound are available in the archived CIF.The H atom of the OH group was located in a difference Fourier map and its coordinates were refined with Uiso = 1.5Ueq(O). All C-bound H atoms were included in calulated positions and refined using a riding model: d(C—H) = 0.95, 1.00, 0.99 and 0.98 Å, for aromatic, methine, methylene and methyl H-atoms, respectively, with Uiso = k × Ueq(C), where k = 1.5 for methyl H atoms, and k = 1.2 for all other H atoms.
There is currently much interest in research into conducting thiophene polymers (Anquetil et al., 2003). Our interest in molecular actuators based on this chemistry led to the isolation of the previously unreported title compound.
In the molecular structure of the title molecule (Fig. 1), the flap atom of the severely flattened C3···C7 ring carries both hydroxy and ethylcarboxylate substituents. Atom C6 lies 0.185 (3) Å from the mean plane through atoms (C3-C5,C7) and this plane is inclined at 4.43 (8) ° to the thiophene ring (S1,C1-C4) mean plane. As a result the dihydrocyclopenta-thiophene-one ring system is also reasonably planar with a r.m.s. deviation of only 0.060 Å from the plane through all 9 non-hydrogen atoms. The C7 atom of the cyclopentane ring carries a phenyl substituent that subtends a dihedral angle of 43.37 (5) ° to the dihydrocyclopentathiophene plane. The Cambridge
Database (CSD, Version 5.32, last update Aug. 2011; Allen, 2002) reveals only three structures involving dihydrocyclopenta-thiophene-one ring systems (Bonini et al., 2004; Chang et al., 2004). In the title molecule the bond distances are normal (Allen et al., 1987) and similar to those reported for these similar molecules.In the crystal O6–H6···O5 hydrogen bonds form inversion dimers with R22(10) ring motifs, (Bernstein et al., 1995), Fig 2. Chains form along c due to weak C11–H11···O5 contacts while C1–H1..O14 contacts form chains at roughly 90 ° to these along b. These contacts combine to generate layers lying parallel to the (100) plane, Fig 3. Inversion dimers also form through weaker R22(12) C7–H7···S1 contacts, and together with C12..H12···O14 hydrogen bonds lead to stacks along b, Fig 4. Additional C15..H15···O6 contacts further stabilize the packing.
For details of conducting thiophene polymers, see: Anquetil et al. (2003). For related structures, see: Bonini et al. (2004); Chang et al. (2004). For details of the Cambridge Structural Database, see: Allen (2002). For hydrogen-bond motifs, see: Bernstein et al. (1995). For standard bond lengths, see Allen et al. (1987). For the preparation of a precursor used in the synthesis, see: Yang (2009).
Data collection: APEX2 (Bruker, 2011); cell
APEX2 and SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip 2010).C16H14O4S | Z = 2 |
Mr = 302.33 | F(000) = 316 |
Triclinic, P1 | Dx = 1.380 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.7407 (4) Å | Cell parameters from 4122 reflections |
b = 9.1005 (4) Å | θ = 2.7–24.9° |
c = 10.5035 (5) Å | µ = 0.24 mm−1 |
α = 84.840 (3)° | T = 91 K |
β = 80.929 (3)° | Block, colourless |
γ = 88.086 (3)° | 0.45 × 0.35 × 0.25 mm |
V = 727.56 (6) Å3 |
Bruker APEXII CCD area-detector diffractometer | 2584 independent reflections |
Radiation source: fine-focus sealed tube | 2233 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
φ and ω scans | θmax = 25.2°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | h = −9→9 |
Tmin = 0.672, Tmax = 0.745 | k = −10→10 |
13007 measured reflections | l = −12→12 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0322P)2 + 0.3338P] where P = (Fo2 + 2Fc2)/3 |
2584 reflections | (Δ/σ)max < 0.001 |
194 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C16H14O4S | γ = 88.086 (3)° |
Mr = 302.33 | V = 727.56 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.7407 (4) Å | Mo Kα radiation |
b = 9.1005 (4) Å | µ = 0.24 mm−1 |
c = 10.5035 (5) Å | T = 91 K |
α = 84.840 (3)° | 0.45 × 0.35 × 0.25 mm |
β = 80.929 (3)° |
Bruker APEXII CCD area-detector diffractometer | 2584 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | 2233 reflections with I > 2σ(I) |
Tmin = 0.672, Tmax = 0.745 | Rint = 0.035 |
13007 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.30 e Å−3 |
2584 reflections | Δρmin = −0.26 e Å−3 |
194 parameters |
Experimental. Spectroscopic data for the title compound: 1H NMR (δ p.p.m., CDCl3, 400 MHz): 8.08 (1H, d, J = 4.8 Hz, CHS), 7.35–7.28 (5H, m, phenyl H), 7.16 (1H, d, J = 4.8 Hz, CHCHS), 4.73 (1H, s, CHC6H5), 4.37 (1H, s, OH), 3.82 & 3.62 [2 x (1H, m, CH2)], 0.85 (3H, t, J = 7 Hz, CH3). IR ν(CO) 1737, 1703 cm-1 . |
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 | ||
S1 | 0.31491 (5) | 0.47012 (4) | 0.41577 (4) | 0.01868 (13) | |
C1 | 0.2877 (2) | 0.33654 (18) | 0.54308 (16) | 0.0206 (4) | |
H1 | 0.3238 | 0.2366 | 0.5349 | 0.025* | |
C2 | 0.2095 (2) | 0.38688 (18) | 0.65715 (16) | 0.0185 (4) | |
H2 | 0.1850 | 0.3271 | 0.7365 | 0.022* | |
C3 | 0.1697 (2) | 0.53999 (17) | 0.64162 (15) | 0.0149 (3) | |
C4 | 0.2184 (2) | 0.59827 (17) | 0.51632 (15) | 0.0155 (3) | |
C5 | 0.1669 (2) | 0.75165 (17) | 0.49802 (15) | 0.0154 (3) | |
O5 | 0.17464 (15) | 0.83394 (12) | 0.39918 (10) | 0.0204 (3) | |
C6 | 0.0911 (2) | 0.79820 (17) | 0.63548 (15) | 0.0152 (3) | |
O6 | −0.07237 (14) | 0.86931 (13) | 0.63575 (12) | 0.0203 (3) | |
H6 | −0.064 (3) | 0.959 (2) | 0.6268 (19) | 0.030* | |
C7 | 0.0721 (2) | 0.65116 (17) | 0.72591 (15) | 0.0158 (3) | |
H7 | −0.0542 | 0.6251 | 0.7382 | 0.019* | |
C8 | 0.1173 (2) | 0.66251 (18) | 0.86036 (15) | 0.0174 (4) | |
C9 | 0.2418 (2) | 0.57266 (19) | 0.91240 (16) | 0.0228 (4) | |
H9 | 0.3044 | 0.5001 | 0.8629 | 0.027* | |
C10 | 0.2752 (3) | 0.5886 (2) | 1.03705 (17) | 0.0293 (4) | |
H10 | 0.3582 | 0.5247 | 1.0728 | 0.035* | |
C11 | 0.1892 (3) | 0.6958 (2) | 1.10879 (17) | 0.0292 (4) | |
H11 | 0.2145 | 0.7074 | 1.1929 | 0.035* | |
C12 | 0.0658 (3) | 0.78667 (19) | 1.05765 (17) | 0.0272 (4) | |
H12 | 0.0067 | 0.8614 | 1.1064 | 0.033* | |
C13 | 0.0281 (2) | 0.76864 (18) | 0.93510 (16) | 0.0216 (4) | |
H13 | −0.0595 | 0.8293 | 0.9017 | 0.026* | |
C14 | 0.2214 (2) | 0.90456 (17) | 0.67132 (14) | 0.0147 (3) | |
O14 | 0.18207 (15) | 1.02944 (12) | 0.69500 (11) | 0.0212 (3) | |
O15 | 0.38114 (14) | 0.84388 (12) | 0.66685 (11) | 0.0200 (3) | |
C15 | 0.5156 (2) | 0.9380 (2) | 0.69937 (17) | 0.0245 (4) | |
H15A | 0.4980 | 1.0404 | 0.6625 | 0.029* | |
H15B | 0.6326 | 0.9028 | 0.6600 | 0.029* | |
C16 | 0.5090 (3) | 0.9368 (3) | 0.8421 (2) | 0.0471 (6) | |
H16A | 0.3957 | 0.9768 | 0.8807 | 0.071* | |
H16B | 0.6030 | 0.9975 | 0.8603 | 0.071* | |
H16C | 0.5241 | 0.8353 | 0.8790 | 0.071* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0229 (2) | 0.0171 (2) | 0.0166 (2) | 0.00254 (17) | −0.00388 (17) | −0.00395 (16) |
C1 | 0.0247 (9) | 0.0143 (8) | 0.0237 (9) | 0.0026 (7) | −0.0072 (7) | −0.0022 (7) |
C2 | 0.0210 (9) | 0.0167 (8) | 0.0179 (8) | −0.0010 (7) | −0.0032 (7) | −0.0007 (7) |
C3 | 0.0122 (8) | 0.0167 (8) | 0.0168 (8) | −0.0012 (6) | −0.0044 (6) | −0.0021 (6) |
C4 | 0.0142 (8) | 0.0158 (8) | 0.0177 (8) | 0.0005 (6) | −0.0046 (6) | −0.0038 (7) |
C5 | 0.0120 (8) | 0.0167 (8) | 0.0185 (9) | −0.0017 (6) | −0.0051 (6) | −0.0023 (7) |
O5 | 0.0252 (7) | 0.0177 (6) | 0.0184 (6) | 0.0006 (5) | −0.0062 (5) | 0.0014 (5) |
C6 | 0.0115 (8) | 0.0155 (8) | 0.0189 (8) | 0.0029 (6) | −0.0031 (6) | −0.0027 (7) |
O6 | 0.0136 (6) | 0.0150 (6) | 0.0327 (7) | 0.0042 (5) | −0.0057 (5) | −0.0029 (5) |
C7 | 0.0128 (8) | 0.0148 (8) | 0.0198 (9) | −0.0012 (6) | −0.0022 (6) | −0.0008 (7) |
C8 | 0.0174 (9) | 0.0167 (8) | 0.0169 (8) | −0.0037 (7) | 0.0015 (7) | −0.0009 (7) |
C9 | 0.0246 (9) | 0.0243 (9) | 0.0194 (9) | 0.0031 (7) | −0.0023 (7) | −0.0050 (7) |
C10 | 0.0317 (11) | 0.0351 (11) | 0.0220 (10) | 0.0013 (9) | −0.0086 (8) | −0.0006 (8) |
C11 | 0.0407 (11) | 0.0329 (11) | 0.0146 (9) | −0.0079 (9) | −0.0034 (8) | −0.0034 (8) |
C12 | 0.0385 (11) | 0.0207 (9) | 0.0199 (9) | −0.0036 (8) | 0.0070 (8) | −0.0066 (7) |
C13 | 0.0234 (9) | 0.0185 (9) | 0.0212 (9) | −0.0008 (7) | 0.0014 (7) | 0.0001 (7) |
C14 | 0.0163 (8) | 0.0157 (8) | 0.0116 (8) | −0.0006 (7) | −0.0003 (6) | −0.0006 (6) |
O14 | 0.0220 (6) | 0.0149 (6) | 0.0270 (7) | 0.0009 (5) | −0.0047 (5) | −0.0034 (5) |
O15 | 0.0118 (6) | 0.0222 (6) | 0.0278 (7) | 0.0012 (5) | −0.0050 (5) | −0.0098 (5) |
C15 | 0.0139 (9) | 0.0281 (10) | 0.0334 (10) | −0.0044 (7) | −0.0040 (7) | −0.0113 (8) |
C16 | 0.0419 (13) | 0.0704 (16) | 0.0341 (12) | −0.0203 (12) | −0.0160 (10) | −0.0069 (11) |
S1—C1 | 1.7164 (17) | C9—C10 | 1.395 (2) |
S1—C4 | 1.7171 (16) | C9—H9 | 0.9500 |
C1—C2 | 1.365 (2) | C10—C11 | 1.376 (3) |
C1—H1 | 0.9500 | C10—H10 | 0.9500 |
C2—C3 | 1.417 (2) | C11—C12 | 1.384 (3) |
C2—H2 | 0.9500 | C11—H11 | 0.9500 |
C3—C4 | 1.374 (2) | C12—C13 | 1.389 (2) |
C3—C7 | 1.509 (2) | C12—H12 | 0.9500 |
C4—C5 | 1.443 (2) | C13—H13 | 0.9500 |
C5—O5 | 1.2190 (19) | C14—O14 | 1.2041 (19) |
C5—C6 | 1.560 (2) | C14—O15 | 1.3332 (19) |
C6—O6 | 1.4018 (18) | O15—C15 | 1.4689 (19) |
C6—C14 | 1.531 (2) | C15—C16 | 1.491 (3) |
C6—C7 | 1.567 (2) | C15—H15A | 0.9900 |
O6—H6 | 0.82 (2) | C15—H15B | 0.9900 |
C7—C8 | 1.520 (2) | C16—H16A | 0.9800 |
C7—H7 | 1.0000 | C16—H16B | 0.9800 |
C8—C9 | 1.389 (2) | C16—H16C | 0.9800 |
C8—C13 | 1.395 (2) | ||
C1—S1—C4 | 89.88 (8) | C8—C9—C10 | 120.27 (16) |
C2—C1—S1 | 113.94 (13) | C8—C9—H9 | 119.9 |
C2—C1—H1 | 123.0 | C10—C9—H9 | 119.9 |
S1—C1—H1 | 123.0 | C11—C10—C9 | 120.64 (17) |
C1—C2—C3 | 111.12 (15) | C11—C10—H10 | 119.7 |
C1—C2—H2 | 124.4 | C9—C10—H10 | 119.7 |
C3—C2—H2 | 124.4 | C10—C11—C12 | 119.60 (16) |
C4—C3—C2 | 112.06 (14) | C10—C11—H11 | 120.2 |
C4—C3—C7 | 112.16 (14) | C12—C11—H11 | 120.2 |
C2—C3—C7 | 135.47 (15) | C11—C12—C13 | 120.06 (16) |
C3—C4—C5 | 112.25 (14) | C11—C12—H12 | 120.0 |
C3—C4—S1 | 112.99 (12) | C13—C12—H12 | 120.0 |
C5—C4—S1 | 134.64 (13) | C12—C13—C8 | 120.82 (17) |
O5—C5—C4 | 130.13 (15) | C12—C13—H13 | 119.6 |
O5—C5—C6 | 124.00 (14) | C8—C13—H13 | 119.6 |
C4—C5—C6 | 105.87 (13) | O14—C14—O15 | 125.38 (15) |
O6—C6—C14 | 109.60 (13) | O14—C14—C6 | 122.73 (14) |
O6—C6—C5 | 111.05 (12) | O15—C14—C6 | 111.83 (13) |
C14—C6—C5 | 106.85 (12) | C14—O15—C15 | 115.81 (12) |
O6—C6—C7 | 110.20 (12) | O15—C15—C16 | 111.60 (15) |
C14—C6—C7 | 113.48 (12) | O15—C15—H15A | 109.3 |
C5—C6—C7 | 105.56 (12) | C16—C15—H15A | 109.3 |
C6—O6—H6 | 111.8 (14) | O15—C15—H15B | 109.3 |
C3—C7—C8 | 119.14 (13) | C16—C15—H15B | 109.3 |
C3—C7—C6 | 102.88 (12) | H15A—C15—H15B | 108.0 |
C8—C7—C6 | 114.66 (13) | C15—C16—H16A | 109.5 |
C3—C7—H7 | 106.4 | C15—C16—H16B | 109.5 |
C8—C7—H7 | 106.4 | H16A—C16—H16B | 109.5 |
C6—C7—H7 | 106.4 | C15—C16—H16C | 109.5 |
C9—C8—C13 | 118.56 (15) | H16A—C16—H16C | 109.5 |
C9—C8—C7 | 123.45 (14) | H16B—C16—H16C | 109.5 |
C13—C8—C7 | 117.99 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O14 | 0.82 (2) | 2.27 (2) | 2.6705 (16) | 110.8 (16) |
O6—H6···O5i | 0.82 (2) | 2.06 (2) | 2.7973 (16) | 150.5 (19) |
C1—H1···O14ii | 0.95 | 2.56 | 3.157 (2) | 121 |
C11—H11···O5iii | 0.95 | 2.52 | 3.386 (2) | 152 |
C15—H15B···O6iv | 0.99 | 2.27 | 3.206 (2) | 157 |
C7—H7···S1v | 1.00 | 2.97 | 3.7855 (16) | 139 |
C12—H12···O14vi | 0.95 | 2.61 | 3.497 (2) | 157 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z; (iii) x, y, z+1; (iv) x+1, y, z; (v) −x, −y+1, −z+1; (vi) −x, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C16H14O4S |
Mr | 302.33 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 91 |
a, b, c (Å) | 7.7407 (4), 9.1005 (4), 10.5035 (5) |
α, β, γ (°) | 84.840 (3), 80.929 (3), 88.086 (3) |
V (Å3) | 727.56 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.24 |
Crystal size (mm) | 0.45 × 0.35 × 0.25 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2011) |
Tmin, Tmax | 0.672, 0.745 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13007, 2584, 2233 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.079, 1.07 |
No. of reflections | 2584 |
No. of parameters | 194 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.26 |
Computer programs: APEX2 (Bruker, 2011), APEX2 and SAINT (Bruker, 2011), SAINT (Bruker, 2011), SHELXS97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999), SHELXL97 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
O6—H6···O14 | 0.82 (2) | 2.27 (2) | 2.6705 (16) | 110.8 (16) |
O6—H6···O5i | 0.82 (2) | 2.06 (2) | 2.7973 (16) | 150.5 (19) |
C1—H1···O14ii | 0.95 | 2.56 | 3.157 (2) | 121 |
C11—H11···O5iii | 0.95 | 2.52 | 3.386 (2) | 152 |
C15—H15B···O6iv | 0.99 | 2.27 | 3.206 (2) | 157 |
C7—H7···S1v | 1.00 | 2.97 | 3.7855 (16) | 139 |
C12—H12···O14vi | 0.95 | 2.61 | 3.497 (2) | 157 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y−1, z; (iii) x, y, z+1; (iv) x+1, y, z; (v) −x, −y+1, −z+1; (vi) −x, −y+2, −z+2. |
Acknowledgements
We thank the New Economy Research Fund (grant No. UOO-X0808) for support of this work and the University of Otago for the purchase of the diffractometer.
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There is currently much interest in research into conducting thiophene polymers (Anquetil et al., 2003). Our interest in molecular actuators based on this chemistry led to the isolation of the previously unreported title compound.
In the molecular structure of the title molecule (Fig. 1), the flap atom of the severely flattened C3···C7 ring carries both hydroxy and ethylcarboxylate substituents. Atom C6 lies 0.185 (3) Å from the mean plane through atoms (C3-C5,C7) and this plane is inclined at 4.43 (8) ° to the thiophene ring (S1,C1-C4) mean plane. As a result the dihydrocyclopenta-thiophene-one ring system is also reasonably planar with a r.m.s. deviation of only 0.060 Å from the plane through all 9 non-hydrogen atoms. The C7 atom of the cyclopentane ring carries a phenyl substituent that subtends a dihedral angle of 43.37 (5) ° to the dihydrocyclopentathiophene plane. The Cambridge Crystal Structure Database (CSD, Version 5.32, last update Aug. 2011; Allen, 2002) reveals only three structures involving dihydrocyclopenta-thiophene-one ring systems (Bonini et al., 2004; Chang et al., 2004). In the title molecule the bond distances are normal (Allen et al., 1987) and similar to those reported for these similar molecules.
In the crystal O6–H6···O5 hydrogen bonds form inversion dimers with R22(10) ring motifs, (Bernstein et al., 1995), Fig 2. Chains form along c due to weak C11–H11···O5 contacts while C1–H1..O14 contacts form chains at roughly 90 ° to these along b. These contacts combine to generate layers lying parallel to the (100) plane, Fig 3. Inversion dimers also form through weaker R22(12) C7–H7···S1 contacts, and together with C12..H12···O14 hydrogen bonds lead to stacks along b, Fig 4. Additional C15..H15···O6 contacts further stabilize the packing.