Abstract
The title compound, C18H12S, contains a thiophene ring which is disordered by rotation of 180° about the linking C—C bond. The site occupancies of the major and minor components of the disordered ring are 0.900 (3) and 0.100 (3), respectively. In one of these disordered components, the molecule is stabilized by an intramolecular C—H⋯S hydrogen bond. The compound was synthesized in good yield (80%) by a modified phase-transfer-catalysed condensation of fluorene with thiophene-2-carbaldehyde.
Related literature
For a related structure, see: Fave et al., 2004 ▶. For related literature, see: Allen (2002 ▶); Lukeš et al. (2003 ▶); Mullen & Wegner (1998 ▶).
Experimental
Crystal data
C18H12S
M r = 260.34
Orthorhombic,
a = 20.757 (4) Å
b = 44.434 (9) Å
c = 5.6260 (11) Å
V = 5189.0 (18) Å3
Z = 16
Mo Kα radiation
μ = 0.23 mm−1
T = 100 (2) K
0.57 × 0.13 × 0.08 mm
Data collection
Oxford Diffraction Gemini R CCD diffractometer
Absorption correction: analytical (Clark & Reid, 1995 ▶) T min = 0.938, T max = 0.985
11725 measured reflections
3018 independent reflections
1903 reflections with I > 2σ(I)
R int = 0.029
Refinement
R[F 2 > 2σ(F 2)] = 0.035
wR(F 2) = 0.090
S = 0.99
3018 reflections
180 parameters
4 restraints
H-atom parameters constrained
Δρmax = 0.15 e Å−3
Δρmin = −0.17 e Å−3
Absolute structure: Flack (1983 ▶), 1110 Friedel pairs
Flack parameter: −0.07 (8)
Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).
Supplementary Material
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807065099/fj2086sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065099/fj2086Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C2—H2A⋯S1A | 0.95 | 2.55 | 3.311 (4) | 139 |
Acknowledgments
The authors thank the Grant Agency of Slovak Republic (grant Nos. 1/2449/05, 1/4453/07 and APVT-20–007304) as well as the Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer.
supplementary crystallographic information
Comment
Our synthetic efforts have been focused on a set of multi-ring monomer systems based on thiophene and fluorene ring system. In this respect, the relationship between the charge transport properties in OFET devices (Mullen & Wegner, 1998) and molecular properties such as redox reversibility and crystal structure have been investigated. As active layers, we used oligomers based on molecules consisting of alternating thiophene and fluorene moieties.
In the title compound (1) the S1—C15 and S1—C18 bond lengths of 1.725 (3) Å and 1.692 (3) Å are in a quite good agreement with similar thiophene compounds in the Cambridge Structural Database (CSD; Version 5.27, 2006 release; Allen, 2002); for example, 2,2',5,5'-tetrakis(2-Thienyl)-3,4:3',4'- bis(tetramethylene)-1,1'-biphosphole (Fave et. al., 2004; CDS refcode BERCIL). The thiophene ring is disordered by rotation about the inter-ring C—C bond. There is one intramolecular C–H···S hydrogen bond.
Experimental
8.3 g (0.05 mol) of fluorene and 5.6 g (0.05 mol) of thiophene-2-carbaldehyde were dissolved in 70 ml of toluene. Then 70 ml 40% NaOH and 2.9 g (0.009 mol) (n-Bu)4N+Br- were added. The resulting heterogenous mixture was vigorously stirred at room temperature for 12 h. After completion of the reaction (TLC control), the water layer was separated, and the organic layer was washed with 100 ml 10% HCl, 300 ml water, 300 ml of brine and dried over Na2SO4. After evaporation of the solvent under reduced pressure, a dark oil was obtained, which was further dissolved in boiling MeOH, decolorized with Norit, filtered and left to cool to room temperature to obtain 10.4 g (80%) of yellow needles m.p.: 75°C (lit. 73–75°C) (Lukeš et al., 2003). The crude product could be purified by column chromatography using silica gel Merck 60 in toluene as an eluent Rf = 0.71 (toluene).
1H NMR (300 MHz, CDCl3 p.p.m.): δ = 8.11 (d, J=7.79 Hz, 1 H), 7.68 – 7.74 (m, 3 H), 7.60 (s, 1 H), 7.42 – 7.45 (m, 2 H), 7.27 – 7.38 (m, 3 H), 7.12 – 7.23 (m, 2 H).
13C-NMR (75 MHz, CDCl3, p.p.m.) δ = 141.19, 139.48, 139.06, 138.91, 136.51, 136.12, 129.25, 128.72, 128.22, 127.57, 127.32, 126.97, 126.82, 124.34, 120.14, 119.74, 119.58, 118.98.
Refinement
H atoms were placed in calculated positions and refined using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2 Ueq(C).
Figures
Fig. 1.
The atomic numbering scheme of 2-(9H-fluoren-9-ylidenemethyl)thiophene. Only the major component of the disordered thiophene ring is shown. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen-bond interactions are indicated by dashed lines.
Crystal data
| C18H12S | F000 = 2176 |
| Mr = 260.34 | Dx = 1.333 Mg m−3 |
| Orthorhombic, Fdd2 | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: F 2 -2d | Cell parameters from 4617 reflections |
| a = 20.757 (4) Å | θ = 3.7–29.1º |
| b = 44.434 (9) Å | µ = 0.23 mm−1 |
| c = 5.6260 (11) Å | T = 100 (2) K |
| V = 5189.0 (18) Å3 | Block, yellow |
| Z = 16 | 0.57 × 0.13 × 0.08 mm |
Data collection
| Oxford Diffraction Gemini R CCD diffractometer | 3018 independent reflections |
| Radiation source: fine-focus sealed tube | 1903 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.029 |
| T = 100(2) K | θmax = 29.1º |
| Rotation method data acquisition using ω and φ scans | θmin = 3.8º |
| Absorption correction: analytical(Clark & Reid, 1995) | h = −27→25 |
| Tmin = 0.938, Tmax = 0.985 | k = −59→58 |
| 11725 measured reflections | l = −7→7 |
Refinement
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.0485P)2] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.090 | (Δ/σ)max < 0.001 |
| S = 0.99 | Δρmax = 0.15 e Å−3 |
| 3018 reflections | Δρmin = −0.17 e Å−3 |
| 180 parameters | Extinction correction: none |
| 4 restraints | Absolute structure: Flack (1983), 1110 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: −0.07 (8) |
| Secondary atom site location: difference Fourier map |
Special details
| Experimental. face-indexed (CrysAlis RED; Oxford Diffraction, 2006) |
| 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| C1 | 0.35040 (9) | 0.03543 (4) | −0.1480 (3) | 0.0504 (5) | |
| C2 | 0.40287 (10) | 0.01668 (4) | −0.1107 (4) | 0.0605 (6) | |
| H2A | 0.4298 | 0.0194 | 0.0241 | 0.073* | |
| C3 | 0.41552 (10) | −0.00616 (5) | −0.2727 (4) | 0.0656 (6) | |
| H3A | 0.4516 | −0.0189 | −0.2475 | 0.079* | |
| C4 | 0.37726 (11) | −0.01069 (5) | −0.4680 (4) | 0.0640 (6) | |
| H4A | 0.3876 | −0.0262 | −0.5781 | 0.077* | |
| C5 | 0.32362 (10) | 0.00724 (4) | −0.5052 (4) | 0.0594 (5) | |
| H5A | 0.2965 | 0.0040 | −0.6387 | 0.071* | |
| C6 | 0.31044 (9) | 0.02985 (4) | −0.3442 (3) | 0.0490 (5) | |
| C7 | 0.25624 (9) | 0.05093 (4) | −0.3394 (3) | 0.0493 (5) | |
| C8 | 0.20399 (10) | 0.05396 (5) | −0.4884 (4) | 0.0607 (5) | |
| H8A | 0.1994 | 0.0413 | −0.6237 | 0.073* | |
| C9 | 0.15827 (11) | 0.07574 (5) | −0.4373 (4) | 0.0670 (6) | |
| H9A | 0.1219 | 0.0780 | −0.5380 | 0.080* | |
| C10 | 0.16522 (10) | 0.09415 (5) | −0.2405 (4) | 0.0658 (6) | |
| H10A | 0.1334 | 0.1090 | −0.2079 | 0.079* | |
| C11 | 0.21746 (10) | 0.09134 (5) | −0.0913 (4) | 0.0608 (5) | |
| H11A | 0.2221 | 0.1043 | 0.0419 | 0.073* | |
| C12 | 0.26339 (9) | 0.06932 (4) | −0.1380 (3) | 0.0490 (5) | |
| C13 | 0.32372 (9) | 0.06148 (4) | −0.0145 (3) | 0.0490 (5) | |
| C14 | 0.34399 (9) | 0.07789 (4) | 0.1761 (3) | 0.0518 (5) | |
| H14A | 0.3125 | 0.0921 | 0.2256 | 0.062* | |
| C15A | 0.40114 (9) | 0.07913 (4) | 0.3214 (3) | 0.0513 (5) | 0.900 (3) |
| C18A | 0.50774 (12) | 0.07874 (5) | 0.5125 (5) | 0.0731 (7) | 0.900 (3) |
| H18A | 0.5513 | 0.0759 | 0.5592 | 0.088* | 0.900 (3) |
| C17A | 0.46607 (12) | 0.09565 (5) | 0.6332 (4) | 0.0670 (6) | 0.900 (3) |
| H17A | 0.4767 | 0.1058 | 0.7767 | 0.080* | 0.900 (3) |
| C16A | 0.4056 (4) | 0.0970 (4) | 0.529 (3) | 0.0747 (14) | 0.900 (3) |
| H16A | 0.3710 | 0.1087 | 0.5900 | 0.090* | 0.900 (3) |
| S1A | 0.47511 (8) | 0.06280 (3) | 0.26734 (16) | 0.0755 (3) | 0.900 (3) |
| C15B | 0.40114 (9) | 0.07913 (4) | 0.3214 (3) | 0.0513 (5) | 0.100 (3) |
| C17B | 0.46607 (12) | 0.09565 (5) | 0.6332 (4) | 0.0670 (6) | 0.100 (3) |
| H17B | 0.4781 | 0.1058 | 0.7750 | 0.080* | 0.100 (3) |
| C18B | 0.50774 (12) | 0.07874 (5) | 0.5125 (5) | 0.0731 (7) | 0.100 (3) |
| H18B | 0.5512 | 0.0758 | 0.5602 | 0.088* | 0.100 (3) |
| C16B | 0.481 (3) | 0.0659 (10) | 0.311 (4) | 0.0755 (3) | 0.100 (3) |
| H16B | 0.5013 | 0.0532 | 0.1960 | 0.091* | 0.100 (3) |
| S1B | 0.3980 (11) | 0.0978 (10) | 0.532 (7) | 0.0747 (14) | 0.100 (3) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0532 (11) | 0.0451 (11) | 0.0528 (11) | −0.0072 (9) | 0.0047 (9) | −0.0017 (9) |
| C2 | 0.0557 (12) | 0.0503 (12) | 0.0754 (13) | −0.0021 (10) | −0.0032 (11) | −0.0117 (11) |
| C3 | 0.0575 (12) | 0.0517 (12) | 0.0874 (16) | 0.0001 (10) | 0.0055 (12) | −0.0126 (12) |
| C4 | 0.0699 (14) | 0.0503 (13) | 0.0717 (13) | −0.0051 (11) | 0.0093 (13) | −0.0153 (12) |
| C5 | 0.0684 (13) | 0.0544 (12) | 0.0555 (11) | −0.0128 (10) | 0.0014 (11) | −0.0072 (11) |
| C6 | 0.0570 (11) | 0.0428 (11) | 0.0473 (10) | −0.0082 (9) | 0.0039 (10) | −0.0004 (9) |
| C7 | 0.0542 (11) | 0.0438 (11) | 0.0500 (11) | −0.0054 (9) | 0.0035 (9) | 0.0041 (10) |
| C8 | 0.0657 (13) | 0.0608 (13) | 0.0557 (10) | −0.0042 (11) | −0.0049 (12) | 0.0017 (11) |
| C9 | 0.0649 (14) | 0.0688 (15) | 0.0673 (15) | −0.0031 (11) | −0.0130 (11) | 0.0128 (12) |
| C10 | 0.0643 (13) | 0.0580 (13) | 0.0750 (14) | 0.0076 (10) | −0.0009 (12) | 0.0077 (13) |
| C11 | 0.0671 (13) | 0.0519 (12) | 0.0634 (12) | 0.0033 (10) | 0.0028 (12) | −0.0026 (11) |
| C12 | 0.0520 (11) | 0.0468 (10) | 0.0483 (11) | −0.0047 (9) | 0.0057 (8) | 0.0018 (9) |
| C13 | 0.0528 (10) | 0.0461 (10) | 0.0482 (11) | −0.0072 (9) | 0.0042 (9) | 0.0000 (9) |
| C14 | 0.0555 (11) | 0.0487 (11) | 0.0513 (11) | −0.0028 (9) | 0.0087 (9) | −0.0005 (9) |
| C15A | 0.0598 (12) | 0.0461 (11) | 0.0480 (11) | −0.0100 (9) | −0.0005 (9) | 0.0023 (9) |
| C18A | 0.0757 (15) | 0.0666 (15) | 0.0771 (14) | −0.0061 (12) | −0.0193 (14) | 0.0019 (14) |
| C17A | 0.0865 (16) | 0.0614 (14) | 0.0531 (12) | −0.0118 (13) | −0.0108 (12) | −0.0052 (12) |
| C16A | 0.082 (3) | 0.0744 (16) | 0.0680 (12) | −0.022 (2) | −0.005 (2) | 0.0022 (11) |
| S1A | 0.0667 (6) | 0.0868 (6) | 0.0731 (5) | 0.0098 (4) | −0.0143 (4) | −0.0252 (5) |
| C15B | 0.0598 (12) | 0.0461 (11) | 0.0480 (11) | −0.0100 (9) | −0.0005 (9) | 0.0023 (9) |
| C17B | 0.0865 (16) | 0.0614 (14) | 0.0531 (12) | −0.0118 (13) | −0.0108 (12) | −0.0052 (12) |
| C18B | 0.0757 (15) | 0.0666 (15) | 0.0771 (14) | −0.0061 (12) | −0.0193 (14) | 0.0019 (14) |
| C16B | 0.0667 (6) | 0.0868 (6) | 0.0731 (5) | 0.0098 (4) | −0.0143 (4) | −0.0252 (5) |
| S1B | 0.082 (3) | 0.0744 (16) | 0.0680 (12) | −0.022 (2) | −0.005 (2) | 0.0022 (11) |
Geometric parameters (Å, °)
| C1—C2 | 1.387 (3) | C10—C11 | 1.377 (3) |
| C1—C6 | 1.403 (3) | C10—H10A | 0.9500 |
| C1—C13 | 1.487 (3) | C11—C12 | 1.391 (3) |
| C2—C3 | 1.389 (3) | C11—H11A | 0.9500 |
| C2—H2A | 0.9500 | C12—C13 | 1.474 (3) |
| C3—C4 | 1.371 (3) | C13—C14 | 1.363 (3) |
| C3—H3A | 0.9500 | C14—C15A | 1.442 (3) |
| C4—C5 | 1.385 (3) | C14—H14A | 0.9500 |
| C4—H4A | 0.9500 | C15A—C16A | 1.416 (19) |
| C5—C6 | 1.380 (3) | C15A—S1A | 1.725 (3) |
| C5—H5A | 0.9500 | C18A—C17A | 1.332 (3) |
| C6—C7 | 1.464 (3) | C18A—S1A | 1.692 (3) |
| C7—C8 | 1.377 (3) | C18A—H18A | 0.9500 |
| C7—C12 | 1.405 (3) | C17A—C16A | 1.388 (3) |
| C8—C9 | 1.386 (3) | C17A—H17A | 0.9500 |
| C8—H8A | 0.9500 | C16A—H16A | 0.9500 |
| C9—C10 | 1.384 (3) | C16B—H16B | 0.9500 |
| C9—H9A | 0.9500 | ||
| C2—C1—C6 | 118.53 (18) | C11—C10—H10A | 119.5 |
| C2—C1—C13 | 133.10 (18) | C9—C10—H10A | 119.5 |
| C6—C1—C13 | 108.35 (17) | C10—C11—C12 | 119.2 (2) |
| C1—C2—C3 | 119.2 (2) | C10—C11—H11A | 120.4 |
| C1—C2—H2A | 120.4 | C12—C11—H11A | 120.4 |
| C3—C2—H2A | 120.4 | C11—C12—C7 | 119.26 (19) |
| C4—C3—C2 | 121.6 (2) | C11—C12—C13 | 131.25 (18) |
| C4—C3—H3A | 119.2 | C7—C12—C13 | 109.45 (17) |
| C2—C3—H3A | 119.2 | C14—C13—C12 | 120.45 (17) |
| C3—C4—C5 | 120.2 (2) | C14—C13—C1 | 134.33 (19) |
| C3—C4—H4A | 119.9 | C12—C13—C1 | 105.19 (16) |
| C5—C4—H4A | 119.9 | C13—C14—C15A | 136.09 (18) |
| C6—C5—C4 | 118.6 (2) | C13—C14—H14A | 112.0 |
| C6—C5—H5A | 120.7 | C15A—C14—H14A | 112.0 |
| C4—C5—H5A | 120.7 | C16A—C15A—C14 | 122.8 (4) |
| C5—C6—C1 | 121.84 (18) | C16A—C15A—S1A | 108.9 (4) |
| C5—C6—C7 | 129.06 (17) | C14—C15A—S1A | 128.03 (14) |
| C1—C6—C7 | 109.09 (16) | C17A—C18A—S1A | 113.1 (2) |
| C8—C7—C12 | 121.16 (18) | C17A—C18A—H18A | 123.5 |
| C8—C7—C6 | 131.03 (19) | S1A—C18A—H18A | 123.5 |
| C12—C7—C6 | 107.78 (17) | C18A—C17A—C16A | 113.4 (9) |
| C7—C8—C9 | 118.8 (2) | C18A—C17A—H17A | 123.3 |
| C7—C8—H8A | 120.6 | C16A—C17A—H17A | 123.3 |
| C9—C8—H8A | 120.6 | C17A—C16A—C15A | 112.5 (12) |
| C10—C9—C8 | 120.5 (2) | C17A—C16A—H16A | 123.8 |
| C10—C9—H9A | 119.8 | C15A—C16A—H16A | 123.8 |
| C8—C9—H9A | 119.8 | C18A—S1A—C15A | 92.08 (13) |
| C11—C10—C9 | 121.1 (2) |
Hydrogen-bond geometry (Å, °)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C2—H2A···S1A | 0.95 | 2.55 | 3.311 (4) | 139 |
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2086).
References
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- Fave, C., Hissler, M., Karpati, T., Rault-Berthelot, J., Deborde, V., Toupet, L., Nyulaszi, L. & Reau, R. (2004). J. Am. Chem. Soc.126, 6058–6059. [DOI] [PubMed]
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- Mullen, K. & Wegner, G. (1998). Electronic Materials: The Oligomer Approach. New York: Wiley.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807065099/fj2086sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536807065099/fj2086Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report