 | Acta Crystallographica Section E Acta Crystallographica Section E CRYSTALLOGRAPHIC COMMUNICATIONS |
journal menu
organic compounds
| CRYSTALLOGRAPHIC COMMUNICATIONS |
access10,11-Dihydrodiindeno[1,2-b:2′,1′-d]thiophene
aWestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland, and bSchool of Chemistry, University of Southampton, Southampton SO17 1BJ, England
*Correspondence e-mail: s.j.coles@soton.ac.uk
The title compound, C18H12S, comprises five fused rings forming an essentially planar molecule, with a total puckering amplitude (Q) of 0.032 Å and a maximum deviation from the mean plane of 0.014 (4) Å for the C atoms of the methylene groups. A crystallographic mirror plane orthogonal to the molecular plane passes through the S atom and the midpoint of the opposite C—C bond within the central five-membered ring. The molecules lie in layers, forming edge-to-face C—H⋯π interactions, with a separation of 2.66 Å between one H atom of the methylene group and the centroid of an adjacent indene ring.
Related literature
For related synthetic chemistry and properties, see: Boberg et al. (1983![[Boberg, F., Czogalla, C.-D., Torges, K.-F. & Wentrup, G.-J. (1983). Liebigs Ann. Chem. 9, 1598-1607.]](../../../../../../logos/arrows/e_arr.gif "Boberg, F., Czogalla, C.-D., Torges, K.-F. & Wentrup, G.-J. (1983). Liebigs Ann. Chem. 9, 1598-1607.")
, 1994); Baierweck et al. (1988). For related structures, see: Klebl et al. (2002); Wong et al. (2006). The puckering amplitude (Q) is defined by Cremer & Pople (1975).
![[Scheme 1]](bi2268scheme1.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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: publCIF (Westrip, 2008).
Supporting information
contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807063684/bi2268sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063684/bi2268Isup2.hkl
The compound was prepared by following a similar methodology to that previously reported (Boberg et al., 1994). Purity of the compound was confirmed by comparison of 1H NMR spectroscopy with that already reported in the literature (Boberg et al., 1983). 1H-NMR (CDC13, δ, p.p.m.): 7.49 (dm, 4H, 3J = 8.4 Hz), 7.33 (t, 2H, 3J = 7.6 Hz), 7.19 (td, 2H, 3J = 7.6 Hz, 4J = 1.2 Hz), 3.73 (s; 4H). M.p.: 559–561 K (lit. 561 K; Baierweck et al. (1988)).
H atoms were fixed in idealized positions [C—H = 0.99 (CH2) or 0.95 Å (CH)] and refined using the riding model with Uiso(H) = 1.2Ueq(C).
The title compound forms an essentially planar molecule with just the two methylene groups deviating significantly from this plane. The maximum deviation from the mean plane of the molecule is 0.014 (4)Å for the methylene atoms and the fused ring system has a total puckering amplitude (Cremer & Pople, 1975) Q = 0.032, providing a further indicator of planarity. There are just two similar structures in the CSD: MUDYIT (Klebl et al., 2002) and SERTUF (Wong et al., 2006). However, these are unsuitable for comparison as they are not planar due to substitution with bulky functional groups at the methylene position.
The molecules lack hydrogen bonding functionality and pack in layers parallel to the (010) planes. Within these layers, one C—H(methylene)···π(indene) contact has a reasonably close separation of 2.66 Å between the H atom and the ring centroid.
For related synthetic chemistry and properties, see: Boberg et al. (1983, 1994); Baierweck et al. (1988). For related structures, see: Klebl et al. (2002); Wong et al. (2006). The puckering amplitude (Q) is defined by Cremer & Pople (1975).
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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: publCIF (Westrip, 2008).
![[Figure 1]](./bi2268fig1thm.gif) | Fig. 1. Molecular structure with 50% probability displacement ellipsoids for non-H atoms. |
| C18H12S | F(000) = 544 |
| Mr = 260.34 | Dx = 1.385 Mg m−3 |
| Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2n | Cell parameters from 9689 reflections |
| a = 8.3358 (6) Å | θ = 2.9–27.5° |
| b = 26.3096 (17) Å | µ = 0.24 mm−1 |
| c = 5.6923 (3) Å | T = 120 K |
| V = 1248.39 (14) Å3 | Plate, colourless |
| Z = 4 | 0.26 × 0.15 × 0.01 mm |
| Bruker–Nonius APEXII CCD diffractometer | 1461 independent reflections |
| Radiation source: Bruker-Nonius FR591 rotating anode | 1201 reflections with I > 2σ(I) |
| 10 cm confocal mirrors monochromator | Rint = 0.064 |
| φ and ω scans | θmax = 27.5°, θmin = 3.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | h = −10→10 |
| Tmin = 0.940, Tmax = 0.998 | k = −34→33 |
| 7885 measured reflections | l = −7→7 |
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.063 | w = 1/[σ2(Fo2) + (0.0523P)2 + 2.4881P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.159 | (Δ/σ)max < 0.001 |
| S = 1.07 | Δρmax = 0.91 e Å−3 |
| 1461 reflections | Δρmin = −0.34 e Å−3 |
| 88 parameters |
| C18H12S | V = 1248.39 (14) Å3 |
| Mr = 260.34 | Z = 4 |
| Orthorhombic, Pnma | Mo Kα radiation |
| a = 8.3358 (6) Å | µ = 0.24 mm−1 |
| b = 26.3096 (17) Å | T = 120 K |
| c = 5.6923 (3) Å | 0.26 × 0.15 × 0.01 mm |
| Bruker–Nonius APEXII CCD diffractometer | 1461 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 1201 reflections with I > 2σ(I) |
| Tmin = 0.940, Tmax = 0.998 | Rint = 0.064 |
| 7885 measured reflections |
| R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
| wR(F2) = 0.159 | H-atom parameters constrained |
| S = 1.07 | Δρmax = 0.91 e Å−3 |
| 1461 reflections | Δρmin = −0.34 e Å−3 |
| 88 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 | 0.3662 (3) | 0.29623 (9) | 0.0799 (4) | 0.0255 (5) | |
| C2 | 0.2804 (3) | 0.27680 (9) | −0.1063 (4) | 0.0242 (5) | |
| C3 | 0.2105 (3) | 0.31895 (9) | −0.2498 (4) | 0.0263 (5) | |
| H3A | 0.0917 | 0.3178 | −0.2492 | 0.032* | |
| H3B | 0.2494 | 0.3178 | −0.414 | 0.032* | |
| C4 | 0.2733 (3) | 0.36587 (10) | −0.1208 (4) | 0.0266 (6) | |
| C5 | 0.2502 (3) | 0.41677 (10) | −0.1715 (5) | 0.0319 (6) | |
| H5 | 0.1889 | 0.4267 | −0.3045 | 0.038* | |
| C6 | 0.3182 (4) | 0.45307 (10) | −0.0244 (5) | 0.0340 (7) | |
| H6 | 0.3034 | 0.4882 | −0.0571 | 0.041* | |
| C7 | 0.4073 (4) | 0.43846 (10) | 0.1690 (5) | 0.0344 (7) | |
| H7 | 0.4524 | 0.4639 | 0.2674 | 0.041* | |
| C8 | 0.4327 (3) | 0.38786 (10) | 0.2235 (5) | 0.0298 (6) | |
| H8 | 0.4946 | 0.3783 | 0.3565 | 0.036* | |
| C9 | 0.3650 (3) | 0.35156 (9) | 0.0778 (4) | 0.0251 (5) | |
| S1 | 0.45076 (12) | 0.25 | 0.25580 (16) | 0.0275 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0217 (12) | 0.0301 (12) | 0.0248 (12) | 0.0012 (10) | 0.0025 (10) | 0.0004 (10) |
| C2 | 0.0216 (12) | 0.0289 (13) | 0.0222 (11) | 0.0005 (10) | 0.0020 (10) | 0.0012 (10) |
| C3 | 0.0263 (13) | 0.0323 (12) | 0.0204 (11) | 0.0013 (10) | −0.0030 (10) | 0.0017 (10) |
| C4 | 0.0224 (12) | 0.0317 (13) | 0.0257 (12) | 0.0000 (10) | 0.0035 (10) | −0.0027 (10) |
| C5 | 0.0340 (15) | 0.0338 (13) | 0.0277 (13) | 0.0035 (12) | 0.0036 (11) | 0.0034 (11) |
| C6 | 0.0383 (16) | 0.0261 (12) | 0.0377 (15) | 0.0022 (12) | 0.0068 (12) | 0.0004 (11) |
| C7 | 0.0348 (16) | 0.0309 (13) | 0.0375 (15) | −0.0018 (11) | 0.0047 (13) | −0.0054 (11) |
| C8 | 0.0259 (13) | 0.0341 (13) | 0.0293 (13) | −0.0004 (11) | 0.0003 (11) | −0.0020 (11) |
| C9 | 0.0202 (12) | 0.0309 (12) | 0.0243 (12) | 0.0017 (10) | 0.0051 (10) | 0.0008 (10) |
| S1 | 0.0278 (5) | 0.0291 (5) | 0.0254 (5) | 0 | −0.0065 (4) | 0 |
| C1—C2 | 1.377 (4) | C5—C6 | 1.391 (4) |
| C1—C9 | 1.456 (3) | C5—H5 | 0.950 |
| C1—S1 | 1.726 (3) | C6—C7 | 1.383 (4) |
| C2—C2i | 1.410 (5) | C6—H6 | 0.950 |
| C2—C3 | 1.496 (3) | C7—C8 | 1.383 (4) |
| C3—C4 | 1.529 (3) | C7—H7 | 0.950 |
| C3—H3A | 0.990 | C8—C9 | 1.385 (4) |
| C3—H3B | 0.990 | C8—H8 | 0.950 |
| C4—C5 | 1.383 (4) | S1—C1i | 1.726 (3) |
| C4—C9 | 1.415 (4) | ||
| C2—C1—C9 | 111.2 (2) | C4—C5—H5 | 120.6 |
| C2—C1—S1 | 113.39 (19) | C6—C5—H5 | 120.6 |
| C9—C1—S1 | 135.4 (2) | C7—C6—C5 | 120.5 (3) |
| C1—C2—C2i | 111.79 (15) | C7—C6—H6 | 119.8 |
| C1—C2—C3 | 110.3 (2) | C5—C6—H6 | 119.8 |
| C2i—C2—C3 | 137.85 (13) | C6—C7—C8 | 121.9 (3) |
| C2—C3—C4 | 101.7 (2) | C6—C7—H7 | 119.1 |
| C2—C3—H3A | 111.4 | C8—C7—H7 | 119.1 |
| C4—C3—H3A | 111.4 | C7—C8—C9 | 117.9 (3) |
| C2—C3—H3B | 111.4 | C7—C8—H8 | 121.1 |
| C4—C3—H3B | 111.4 | C9—C8—H8 | 121.1 |
| H3A—C3—H3B | 109.3 | C8—C9—C4 | 121.0 (2) |
| C5—C4—C9 | 120.0 (2) | C8—C9—C1 | 133.0 (2) |
| C5—C4—C3 | 129.3 (2) | C4—C9—C1 | 106.0 (2) |
| C9—C4—C3 | 110.7 (2) | C1i—S1—C1 | 89.61 (17) |
| C4—C5—C6 | 118.8 (3) | ||
| C9—C1—C2—C2i | −179.91 (15) | C7—C8—C9—C4 | 0.2 (4) |
| S1—C1—C2—C2i | 0.9 (2) | C7—C8—C9—C1 | 179.9 (3) |
| C9—C1—C2—C3 | −1.0 (3) | C5—C4—C9—C8 | −0.1 (4) |
| S1—C1—C2—C3 | 179.78 (18) | C3—C4—C9—C8 | −179.2 (2) |
| C1—C2—C3—C4 | 1.5 (3) | C5—C4—C9—C1 | −179.8 (2) |
| C2i—C2—C3—C4 | 179.98 (13) | C3—C4—C9—C1 | 1.0 (3) |
| C2—C3—C4—C5 | 179.4 (3) | C2—C1—C9—C8 | −179.7 (3) |
| C2—C3—C4—C9 | −1.5 (3) | S1—C1—C9—C8 | −0.7 (5) |
| C9—C4—C5—C6 | 0.0 (4) | C2—C1—C9—C4 | 0.0 (3) |
| C3—C4—C5—C6 | 179.0 (3) | S1—C1—C9—C4 | 179.0 (2) |
| C4—C5—C6—C7 | 0.0 (4) | C2—C1—S1—C1i | −1.1 (3) |
| C5—C6—C7—C8 | 0.2 (4) | C9—C1—S1—C1i | 179.9 (2) |
| C6—C7—C8—C9 | −0.3 (4) |
| Symmetry code: (i) x, −y+1/2, z. |
Experimental details
| Crystal data | |
| Chemical formula | C18H12S |
| Mr | 260.34 |
| Crystal system, space group | Orthorhombic, Pnma |
| Temperature (K) | 120 |
| a, b, c (Å) | 8.3358 (6), 26.3096 (17), 5.6923 (3) |
| V (Å3) | 1248.39 (14) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.24 |
| Crystal size (mm) | 0.26 × 0.15 × 0.01 |
| Data collection | |
| Diffractometer | Bruker–Nonius APEXII CCD |
| Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) |
| Tmin, Tmax | 0.940, 0.998 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 7885, 1461, 1201 |
| Rint | 0.064 |
| (sin θ/λ)max (Å−1) | 0.649 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.159, 1.07 |
| No. of reflections | 1461 |
| No. of parameters | 88 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.91, −0.34 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), publCIF (Westrip, 2008).
Acknowledgements
The authors thank the EPSRC for funding the National Crystallographic Service (Southampton, England). PJS and AK thank the EPSRC (GR/T28379) for funding.
References
Baierweck, P., Simmross, U. & Müllen, K. (1988). Chem. Ber. 121, 2195–2200. CrossRef CAS Web of Science Google Scholar
Boberg, F., Czogalla, C.-D., Torges, K.-F. & Wentrup, G.-J. (1983). Liebigs Ann. Chem. 9, 1598–1607. CrossRef Google Scholar
Boberg, F., Deters, K., Schulz, J. & Torges, K.-F. (1994). Phosphorus Sulfur Silicon Relat. Elem. 91, 69–80. CrossRef CAS Web of Science Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Klebl, I., Gompper, R. & Polborn, K. (2002). Private communication (refcode MUDYIT). CCDC, Union Road, Cambridge, England. Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2007). SADABS. Version 2007/2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar
Wong, K.-T., Chao, T.-C., Chi, L.-C., Chu, Y.-Y., Balaiah, A., Chiu, S.-F., Liu, Y.-H. & Wang, Y. (2006). Org. Lett. 8, 5033–5037. Web of Science CSD CrossRef PubMed CAS Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
| CRYSTALLOGRAPHIC COMMUNICATIONS |
The title compound forms an essentially planar molecule with just the two methylene groups deviating significantly from this plane. The maximum deviation from the mean plane of the molecule is 0.014 (4)Å for the methylene atoms and the fused ring system has a total puckering amplitude (Cremer & Pople, 1975) Q = 0.032, providing a further indicator of planarity. There are just two similar structures in the CSD: MUDYIT (Klebl et al., 2002) and SERTUF (Wong et al., 2006). However, these are unsuitable for comparison as they are not planar due to substitution with bulky functional groups at the methylene position.
The molecules lack hydrogen bonding functionality and pack in layers parallel to the (010) planes. Within these layers, one C—H(methylene)···π(indene) contact has a reasonably close separation of 2.66 Å between the H atom and the ring centroid.