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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o167.
Published online 2007 December 6. doi:  10.1107/S1600536807063684
PMCID: PMC2915234

10,11-Dihydro­diindeno[1,2-b:2′,1′-d]thio­phene

Abstract

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 [triangle], 1994 [triangle]); Baierweck et al. (1988 [triangle]). For related structures, see: Klebl et al. (2002 [triangle]); Wong et al. (2006 [triangle]). The puckering amplitude (Q) is defined by Cremer & Pople (1975 [triangle]).

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Object name is e-64-0o167-scheme1.jpg

Experimental

Crystal data

  • C18H12S
  • M r = 260.34
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o167-efi1.jpg
  • 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 [triangle]) T min = 0.940, T max = 0.998
  • 7885 measured reflections
  • 1461 independent reflections
  • 1201 reflections with I > 2σ(I)
  • R int = 0.064

Refinement

  • R[F 2 > 2σ(F 2)] = 0.063
  • wR(F 2) = 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 [triangle]); cell refinement: DENZO (Otwinowski & Minor, 1997 [triangle]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063684/bi2268sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063684/bi2268Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the EPSRC for funding the National Crystallographic Service (Southampton, England). PJS and AK thank the EPSRC (GR/T28379) for funding.

supplementary crystallographic information

Comment

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.

Experimental

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

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).

Figures

Fig. 1.
Molecular structure with 50% probability displacement ellipsoids for non-H atoms.

Crystal data

C18H12SF000 = 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 = 2.9–27.5º
b = 26.3096 (17) ŵ = 0.24 mm1
c = 5.6923 (3) ÅT = 120 (2) K
V = 1248.39 (14) Å3Plate, colourless
Z = 40.26 × 0.15 × 0.01 mm

Data collection

Bruker–Nonius APEXII CCD diffractometer1461 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode1201 reflections with I > 2σ(I)
Monochromator: 10 cm confocal mirrorsRint = 0.064
T = 120(2) Kθmax = 27.5º
[var phi] and ω scansθmin = 3.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 2007)h = −10→10
Tmin = 0.940, Tmax = 0.998k = −34→33
7885 measured reflectionsl = −7→7

Refinement

Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0523P)2 + 2.4881P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.063(Δ/σ)max < 0.001
wR(F2) = 0.159Δρmax = 0.91 e Å3
S = 1.07Δρmin = −0.34 e Å3
1461 reflectionsExtinction correction: none
88 parameters

Special details

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)

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)
H3A0.09170.3178−0.24920.032*
H3B0.24940.3178−0.4140.032*
C40.2733 (3)0.36587 (10)−0.1208 (4)0.0266 (6)
C50.2502 (3)0.41677 (10)−0.1715 (5)0.0319 (6)
H50.18890.4267−0.30450.038*
C60.3182 (4)0.45307 (10)−0.0244 (5)0.0340 (7)
H60.30340.4882−0.05710.041*
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)

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)0−0.0065 (4)0

Geometric parameters (Å, °)

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—C2i−179.91 (15)C7—C8—C9—C40.2 (4)
S1—C1—C2—C2i0.9 (2)C7—C8—C9—C1179.9 (3)
C9—C1—C2—C3−1.0 (3)C5—C4—C9—C8−0.1 (4)
S1—C1—C2—C3179.78 (18)C3—C4—C9—C8−179.2 (2)
C1—C2—C3—C41.5 (3)C5—C4—C9—C1−179.8 (2)
C2i—C2—C3—C4179.98 (13)C3—C4—C9—C11.0 (3)
C2—C3—C4—C5179.4 (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—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—C1i−1.1 (3)
C5—C6—C7—C80.2 (4)C9—C1—S1—C1i179.9 (2)
C6—C7—C8—C9−0.3 (4)

Symmetry codes: (i) x, −y+1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2268).

References

  • Baierweck, P., Simmross, U. & Müllen, K. (1988). Chem. Ber.121, 2195–2200.
  • Boberg, F., Czogalla, C.-D., Torges, K.-F. & Wentrup, G.-J. (1983). Liebigs Ann. Chem.9, 1598–1607.
  • Boberg, F., Deters, K., Schulz, J. & Torges, K.-F. (1994). Phosphorus Sulfur Silicon Relat. Elem.91, 69–80.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc.97, 1354–1358.
  • Klebl, I., Gompper, R. & Polborn, K. (2002). Private communication (refcode MUDYIT). CCDC, Union Road, Cambridge, England.
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  • 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.
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  • Westrip, S. P. (2008). publCIF In preparation.
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