organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

10,11-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

(Received 20 November 2007; accepted 27 November 2007; online 6 December 2007)

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.], 1994[Boberg, F., Deters, K., Schulz, J. & Torges, K.-F. (1994). Phosphorus Sulfur Silicon Relat. Elem. 91, 69-80.]); Baierweck et al. (1988[Baierweck, P., Simmross, U. & Müllen, K. (1988). Chem. Ber. 121, 2195-2200.]). For related structures, see: Klebl et al. (2002[Klebl, I., Gompper, R. & Polborn, K. (2002). Private communication (refcode MUDYIT). CCDC, Union Road, Cambridge, England.]); Wong et al. (2006[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.]). The puckering amplitude (Q) is defined by Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]).

[Scheme 1]

Experimental

Crystal data
  • C18H12S

  • Mr = 260.34

  • Orthorhombic, P n m a

  • a = 8.3358 (6) Å

  • b = 26.3096 (17) Å

  • c = 5.6923 (3) Å

  • V = 1248.39 (14) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.24 mm−1

  • T = 120 (2) K

  • 0.26 × 0.15 × 0.01 mm

Data collection
  • Bruker–Nonius APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2007[Sheldrick, G. M. (2007). SADABS. Version 2007/2. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.940, Tmax = 0.998

  • 7885 measured reflections

  • 1461 independent reflections

  • 1201 reflections with I > 2σ(I)

  • Rint = 0.064

Refinement
  • R[F2 > 2σ(F2)] = 0.063

  • wR(F2) = 0.159

  • S = 1.07

  • 1461 reflections

  • 88 parameters

  • H-atom parameters constrained

  • Δρmax = 0.91 e Å−3

  • Δρmin = −0.34 e Å−3

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[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.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: publCIF (Westrip, 2008[Westrip, S. P. (2008). publCIF. In preparation.]).

Supporting information


Comment top

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.

Related literature top

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).

Experimental top

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)).

Refinement top

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).

Structure description top

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).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: 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).

Figures top
[Figure 1] Fig. 1. Molecular structure with 50% probability displacement ellipsoids for non-H atoms.
10,11-Dihydrodiindeno[1,2 - b:2',1'-d]thiophene top
Crystal data top
C18H12SF(000) = 544
Mr = 260.34Dx = 1.385 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 9689 reflections
a = 8.3358 (6) Åθ = 2.9–27.5°
b = 26.3096 (17) ŵ = 0.24 mm1
c = 5.6923 (3) ÅT = 120 K
V = 1248.39 (14) Å3Plate, colourless
Z = 40.26 × 0.15 × 0.01 mm
Data collection top
Bruker–Nonius APEXII CCD
diffractometer
1461 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1201 reflections with I > 2σ(I)
10 cm confocal mirrors monochromatorRint = 0.064
φ and ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
h = 1010
Tmin = 0.940, Tmax = 0.998k = 3433
7885 measured reflectionsl = 77
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-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 = 1.07Δρmax = 0.91 e Å3
1461 reflectionsΔρmin = 0.34 e Å3
88 parameters
Crystal data top
C18H12SV = 1248.39 (14) Å3
Mr = 260.34Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 8.3358 (6) ŵ = 0.24 mm1
b = 26.3096 (17) ÅT = 120 K
c = 5.6923 (3) Å0.26 × 0.15 × 0.01 mm
Data collection top
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 = 0.998Rint = 0.064
7885 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.159H-atom parameters constrained
S = 1.07Δρmax = 0.91 e Å3
1461 reflectionsΔρmin = 0.34 e Å3
88 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3662 (3)0.29623 (9)0.0799 (4)0.0255 (5)
C20.2804 (3)0.27680 (9)0.1063 (4)0.0242 (5)
C30.2105 (3)0.31895 (9)0.2498 (4)0.0263 (5)
H3A0.09170.31780.24920.032*
H3B0.24940.31780.4140.032*
C40.2733 (3)0.36587 (10)0.1208 (4)0.0266 (6)
C50.2502 (3)0.41677 (10)0.1715 (5)0.0319 (6)
H50.18890.42670.30450.038*
C60.3182 (4)0.45307 (10)0.0244 (5)0.0340 (7)
H60.30340.48820.05710.041*
C70.4073 (4)0.43846 (10)0.1690 (5)0.0344 (7)
H70.45240.46390.26740.041*
C80.4327 (3)0.38786 (10)0.2235 (5)0.0298 (6)
H80.49460.37830.35650.036*
C90.3650 (3)0.35156 (9)0.0778 (4)0.0251 (5)
S10.45076 (12)0.250.25580 (16)0.0275 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0217 (12)0.0301 (12)0.0248 (12)0.0012 (10)0.0025 (10)0.0004 (10)
C20.0216 (12)0.0289 (13)0.0222 (11)0.0005 (10)0.0020 (10)0.0012 (10)
C30.0263 (13)0.0323 (12)0.0204 (11)0.0013 (10)0.0030 (10)0.0017 (10)
C40.0224 (12)0.0317 (13)0.0257 (12)0.0000 (10)0.0035 (10)0.0027 (10)
C50.0340 (15)0.0338 (13)0.0277 (13)0.0035 (12)0.0036 (11)0.0034 (11)
C60.0383 (16)0.0261 (12)0.0377 (15)0.0022 (12)0.0068 (12)0.0004 (11)
C70.0348 (16)0.0309 (13)0.0375 (15)0.0018 (11)0.0047 (13)0.0054 (11)
C80.0259 (13)0.0341 (13)0.0293 (13)0.0004 (11)0.0003 (11)0.0020 (11)
C90.0202 (12)0.0309 (12)0.0243 (12)0.0017 (10)0.0051 (10)0.0008 (10)
S10.0278 (5)0.0291 (5)0.0254 (5)00.0065 (4)0
Geometric parameters (Å, º) top
C1—C21.377 (4)C5—C61.391 (4)
C1—C91.456 (3)C5—H50.950
C1—S11.726 (3)C6—C71.383 (4)
C2—C2i1.410 (5)C6—H60.950
C2—C31.496 (3)C7—C81.383 (4)
C3—C41.529 (3)C7—H70.950
C3—H3A0.990C8—C91.385 (4)
C3—H3B0.990C8—H80.950
C4—C51.383 (4)S1—C1i1.726 (3)
C4—C91.415 (4)
C2—C1—C9111.2 (2)C4—C5—H5120.6
C2—C1—S1113.39 (19)C6—C5—H5120.6
C9—C1—S1135.4 (2)C7—C6—C5120.5 (3)
C1—C2—C2i111.79 (15)C7—C6—H6119.8
C1—C2—C3110.3 (2)C5—C6—H6119.8
C2i—C2—C3137.85 (13)C6—C7—C8121.9 (3)
C2—C3—C4101.7 (2)C6—C7—H7119.1
C2—C3—H3A111.4C8—C7—H7119.1
C4—C3—H3A111.4C7—C8—C9117.9 (3)
C2—C3—H3B111.4C7—C8—H8121.1
C4—C3—H3B111.4C9—C8—H8121.1
H3A—C3—H3B109.3C8—C9—C4121.0 (2)
C5—C4—C9120.0 (2)C8—C9—C1133.0 (2)
C5—C4—C3129.3 (2)C4—C9—C1106.0 (2)
C9—C4—C3110.7 (2)C1i—S1—C189.61 (17)
C4—C5—C6118.8 (3)
C9—C1—C2—C2i179.91 (15)C7—C8—C9—C40.2 (4)
S1—C1—C2—C2i0.9 (2)C7—C8—C9—C1179.9 (3)
C9—C1—C2—C31.0 (3)C5—C4—C9—C80.1 (4)
S1—C1—C2—C3179.78 (18)C3—C4—C9—C8179.2 (2)
C1—C2—C3—C41.5 (3)C5—C4—C9—C1179.8 (2)
C2i—C2—C3—C4179.98 (13)C3—C4—C9—C11.0 (3)
C2—C3—C4—C5179.4 (3)C2—C1—C9—C8179.7 (3)
C2—C3—C4—C91.5 (3)S1—C1—C9—C80.7 (5)
C9—C4—C5—C60.0 (4)C2—C1—C9—C40.0 (3)
C3—C4—C5—C6179.0 (3)S1—C1—C9—C4179.0 (2)
C4—C5—C6—C70.0 (4)C2—C1—S1—C1i1.1 (3)
C5—C6—C7—C80.2 (4)C9—C1—S1—C1i179.9 (2)
C6—C7—C8—C90.3 (4)
Symmetry code: (i) x, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC18H12S
Mr260.34
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)120
a, b, c (Å)8.3358 (6), 26.3096 (17), 5.6923 (3)
V3)1248.39 (14)
Z4
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.26 × 0.15 × 0.01
Data collection
DiffractometerBruker–Nonius APEXII CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2007)
Tmin, Tmax0.940, 0.998
No. of measured, independent and
observed [I > 2σ(I)] reflections
7885, 1461, 1201
Rint0.064
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.159, 1.07
No. of reflections1461
No. of parameters88
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationBaierweck, P., Simmross, U. & Müllen, K. (1988). Chem. Ber. 121, 2195–2200.  CrossRef CAS Web of Science Google Scholar
First citationBoberg, F., Czogalla, C.-D., Torges, K.-F. & Wentrup, G.-J. (1983). Liebigs Ann. Chem. 9, 1598–1607.  CrossRef Google Scholar
First citationBoberg, F., Deters, K., Schulz, J. & Torges, K.-F. (1994). Phosphorus Sulfur Silicon Relat. Elem. 91, 69–80.  CrossRef CAS Web of Science Google Scholar
First citationCremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.  CrossRef CAS Web of Science Google Scholar
First citationKlebl, I., Gompper, R. & Polborn, K. (2002). Private communication (refcode MUDYIT). CCDC, Union Road, Cambridge, England.  Google Scholar
First citationNonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationOtwinowski, 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
First citationSheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2007). SADABS. Version 2007/2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2008). publCIF. In preparation.  Google Scholar
First citationWong, 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

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ISSN: 2056-9890
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