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accessBis(2-thienyl)acetylene
aDepartment of Chemistry, Mount Holyoke College, South Hadley, MA 01075, USA, and bExilica Limited, The Technocentre, Puma Way, Coventry CV1 2TT, UK
*Correspondence e-mail: hamilton@mtholyoke.edu
The planar [maximum deviation 0.0066 (4) Å] symmetrical molecule of the title compound, C10H6S2, lies across a crystallographic inversion centre. The thiophene rings are rotationally disordered about the acetylene bond, with the two pseudo inversion-related S atoms in 0.80:0.20 occupancy sites. The C≡C bond distance is 1.195 (9) Å.
Related literature
For the preparation of the title compound, related diarylacetylenes and cobalt-containing derived from these materials, see: Harrison et al. (1997![[Harrison, R. M., Brotin, T., Noll, B. C. & Michl, J. (1997). Organometallics, 16, 3401-3412.]](../../../../../../logos/arrows/e_arr.gif "Harrison, R. M., Brotin, T., Noll, B. C. & Michl, J. (1997). Organometallics, 16, 3401-3412.")
); Harcourt et al. (2008). For recent synthetic organic uses, see: Yu & Rovis (2006); Geyer et al. (2008). The metal center employed in an acetylene cyclooligomerization may also remain as an integral component of the product, or products, see: Rausch & Genetti (1970). For spectroscopic data, see: Mio et al. (2002).
![[Scheme 1]](zs2008scheme1.gif)
Experimental
Crystal data
|
Data collection: COLLECT (Nonius, 1998); cell DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536809036812/zs2008sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536809036812/zs2008Isup2.hkl
The title compound was prepared by Sonogashira coupling of two equivalents of 2-iodothiophene to acetylene under standard conditions (Harrison et al., 1997). Full experimental details (Harcourt et al., 2008) and spectroscopic data (Mio et al., 2002) have been previously published.
All H atoms were included in the at calculated positions, in the riding-model approximation, with C—H distances of 0.95 Å. The isotropic displacement parameters for all H atoms were set equal to 1.25Ueq of the The refined site occupancy factors for the disordered atoms (S1, C3, H3) and (S3, C1, H1) of the pseudo-centrosymmetrically related thiophene rings were 0.80 (1), and 0.20 (1) respectively. file checks indicate that there is only one listed reflection that is likely to have been affected by the beamstop.
Diarylacetylenes are versatile components of metal-mediated reactions. Their relative ease of preparation from palladium catalyzed coupling of aryl iodides to acetylene has ensured their continued use in the development of new synthetic routes, for example, nitrogen containing heterocycles (Yu & Rovis, 2006), and new catalytic reaction methodologies such as alkyne–nitrile cross metathesis (Geyer et al., 2008). The metal center employed in an acetylene cyclooligomerization may also remain as an integral component of the product, or products, as described in the seminal work of Rausch & Genetti (1970). The title compound bis(2-thienyl)acetylene (I) is found to have inversion symmetry coincident with (Fig. 1). However, the two 2-thiophene residues are rotationally disordered about the acetylene bond with the two pseudo-inversion related S atoms having 80/20% occupancy. The C—C triple bond distance is 1.195 (9) Å.
For the preparation of the title compound, related diarylacetylenes and cobalt-containing derived from these materials, see: Harrison et al. (1997); Harcourt et al. (2008). For recent synthetic organic uses, see: Yu & Rovis (2006); Geyer et al. (2008). The metal center employed in an acetylene cyclooligomerization may also remain as an integral component of the product, or products, see: Rausch & Genetti (1970). For spectroscopic data, see: Mio et al. (2002);
Data collection: COLLECT (Nonius, 1998); cell DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./zs2008fig1thm.gif) | Fig. 1. Molecular configuration and atom-numbering scheme for (I) showing inversion symmetry [symmetry code: (a) -x, -y + 1, -z]. Rotationally disordered thiophene S/C atom pairs are S1, C3 (S.O.F. 0.80) and S3, C1 (S.O.F. 0.20). Displacement ellipsoids are drawn at the 50% probability level. |
| C10H6S2 | F(000) = 392 |
| Mr = 190.29 | Dx = 1.446 Mg m−3 |
| Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2n 2ab | Cell parameters from 1041 reflections |
| a = 10.6325 (15) Å | θ = 1.0–27.5° |
| b = 10.8713 (15) Å | µ = 0.54 mm−1 |
| c = 7.5600 (5) Å | T = 120 K |
| V = 873.85 (18) Å3 | Needle, colourless |
| Z = 4 | 0.55 × 0.05 × 0.03 mm |
| Nonius KappaCCD diffractometer | 849 independent reflections |
| Radiation source: Bruker Nonius FR591 rotating anode | 493 reflections with I > 2σ(I) |
| 10 cm confocal mirrors monochromator | Rint = 0.129 |
| Detector resolution: 9.091 pixels mm-1 | θmax = 26.0°, θmin = 2.7° |
| φ and ω scans | h = −13→11 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→12 |
| Tmin = 0.755, Tmax = 0.984 | l = −9→8 |
| 3812 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)] = 0.073 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.173 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.050P)2 + 3.1085P] where P = (Fo2 + 2Fc2)/3 |
| 849 reflections | (Δ/σ)max < 0.001 |
| 58 parameters | Δρmax = 0.41 e Å−3 |
| 0 restraints | Δρmin = −0.41 e Å−3 |
| C10H6S2 | V = 873.85 (18) Å3 |
| Mr = 190.29 | Z = 4 |
| Orthorhombic, Pbcn | Mo Kα radiation |
| a = 10.6325 (15) Å | µ = 0.54 mm−1 |
| b = 10.8713 (15) Å | T = 120 K |
| c = 7.5600 (5) Å | 0.55 × 0.05 × 0.03 mm |
| Nonius KappaCCD diffractometer | 849 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 493 reflections with I > 2σ(I) |
| Tmin = 0.755, Tmax = 0.984 | Rint = 0.129 |
| 3812 measured reflections |
| R[F2 > 2σ(F2)] = 0.073 | 0 restraints |
| wR(F2) = 0.173 | H-atom parameters constrained |
| S = 1.08 | Δρmax = 0.41 e Å−3 |
| 849 reflections | Δρmin = −0.41 e Å−3 |
| 58 parameters |
Experimental. The minimum and maximum absorption values stated above are those calculated in SHELXL97 from the given crystal dimensions. The ratio of minimum to maximum apparent transmission was determined experimentally as 0.675726. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| S1 | 0.17278 (13) | 0.28773 (15) | 0.17139 (19) | 0.0303 (6) | 0.80 |
| C1 | 0.17278 (13) | 0.28773 (15) | 0.17139 (19) | 0.0303 (6) | 0.20 |
| H1 | 0.1105 | 0.2380 | 0.2263 | 0.038* | 0.20 |
| C2 | 0.1671 (4) | 0.4188 (5) | 0.0513 (6) | 0.0220 (12) | |
| C3 | 0.2949 (3) | 0.4642 (3) | −0.0126 (4) | 0.0291 (9) | 0.80 |
| H3 | 0.3142 | 0.5342 | −0.0827 | 0.036* | 0.80 |
| S3 | 0.2949 (3) | 0.4642 (3) | −0.0126 (4) | 0.0291 (9) | 0.20 |
| C4 | 0.3820 (5) | 0.3703 (5) | 0.0635 (6) | 0.0295 (15) | |
| H4 | 0.4705 | 0.3749 | 0.0468 | 0.037* | |
| C5 | 0.3285 (4) | 0.2786 (5) | 0.1572 (6) | 0.0271 (13) | |
| H5 | 0.3757 | 0.2144 | 0.2105 | 0.034* | |
| C6 | 0.0498 (4) | 0.4768 (5) | 0.0149 (6) | 0.0235 (14) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0283 (8) | 0.0314 (11) | 0.0311 (8) | 0.0002 (8) | −0.0017 (6) | 0.0030 (7) |
| C1 | 0.0283 (8) | 0.0314 (11) | 0.0311 (8) | 0.0002 (8) | −0.0017 (6) | 0.0030 (7) |
| C2 | 0.022 (2) | 0.023 (3) | 0.021 (2) | −0.001 (2) | −0.0019 (19) | 0.000 (2) |
| C3 | 0.0264 (16) | 0.029 (2) | 0.0322 (16) | 0.0028 (17) | −0.0049 (13) | −0.0064 (15) |
| S3 | 0.0264 (16) | 0.029 (2) | 0.0322 (16) | 0.0028 (17) | −0.0049 (13) | −0.0064 (15) |
| C4 | 0.021 (2) | 0.035 (4) | 0.032 (3) | −0.002 (3) | 0.003 (2) | −0.008 (3) |
| C5 | 0.030 (3) | 0.027 (3) | 0.025 (2) | 0.012 (3) | −0.007 (2) | −0.006 (2) |
| C6 | 0.025 (2) | 0.021 (4) | 0.025 (2) | −0.002 (2) | −0.001 (2) | −0.001 (2) |
| S1—C2 | 1.691 (5) | C4—C5 | 1.349 (7) |
| C2—C6 | 1.424 (6) | C4—H4 | 0.95 |
| C2—C3 | 1.525 (5) | C5—H5 | 0.95 |
| C3—C4 | 1.493 (6) | C6—C6i | 1.195 (9) |
| C3—H3 | 0.95 | ||
| C6—C2—C3 | 125.2 (4) | C5—C4—C3 | 116.4 (4) |
| C6—C2—S1 | 120.5 (4) | C5—C4—H4 | 121.8 |
| C3—C2—S1 | 114.2 (3) | C3—C4—H4 | 121.8 |
| C4—C3—C2 | 102.1 (3) | C4—C5—H5 | 122.9 |
| C4—C3—H3 | 128.9 | C6i—C6—C2 | 178.7 (7) |
| C2—C3—H3 | 128.9 | ||
| C6—C2—C3—C4 | 179.9 (4) | C2—C3—C4—C5 | 0.8 (5) |
| S1—C2—C3—C4 | −1.1 (4) |
| Symmetry code: (i) −x, −y+1, −z. |
Experimental details
| Crystal data | |
| Chemical formula | C10H6S2 |
| Mr | 190.29 |
| Crystal system, space group | Orthorhombic, Pbcn |
| Temperature (K) | 120 |
| a, b, c (Å) | 10.6325 (15), 10.8713 (15), 7.5600 (5) |
| V (Å3) | 873.85 (18) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.54 |
| Crystal size (mm) | 0.55 × 0.05 × 0.03 |
| Data collection | |
| Diffractometer | Nonius KappaCCD |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
| Tmin, Tmax | 0.755, 0.984 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 3812, 849, 493 |
| Rint | 0.129 |
| (sin θ/λ)max (Å−1) | 0.617 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.073, 0.173, 1.08 |
| No. of reflections | 849 |
| No. of parameters | 58 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.41, −0.41 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
Acknowledgements
We thank the Donors of the American Chemical Society Petroleum Research Fund (Award 45312), the Camille and Henry Dreyfus Foundation (Henry Dreyfus Teacher Scholar Award to DGH, 2005–2010) and the EPSRC National Crystallography Service (University of Southampton, UK) for their support of this work.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Diarylacetylenes are versatile components of metal-mediated cycloaddition reactions. Their relative ease of preparation from palladium catalyzed coupling of aryl iodides to acetylene has ensured their continued use in the development of new synthetic routes, for example, nitrogen containing heterocycles (Yu & Rovis, 2006), and new catalytic reaction methodologies such as alkyne–nitrile cross metathesis (Geyer et al., 2008). The metal center employed in an acetylene cyclooligomerization may also remain as an integral component of the product, or products, as described in the seminal work of Rausch & Genetti (1970). The title compound bis(2-thienyl)acetylene (I) is found to have inversion symmetry coincident with crystallographic symmetry (Fig. 1). However, the two 2-thiophene residues are rotationally disordered about the acetylene bond with the two pseudo-inversion related S atoms having 80/20% occupancy. The C—C triple bond distance is 1.195 (9) Å.