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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807065099/fj2086sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807065099/fj2086Isup2.hkl
Contains datablock I

CCDC reference: 674570

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.003 Å
  • Disorder in main residue
  • R factor = 0.034
  • wR factor = 0.090
  • Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT230_ALERT_2_B Hirshfeld Test Diff for C15A - C16A .. 9.62 su PLAT230_ALERT_2_B Hirshfeld Test Diff for C16A - C15B .. 9.62 su PLAT230_ALERT_2_B Hirshfeld Test Diff for S1B - C15B .. 10.72 su
Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for S1A - C18A .. 6.54 su PLAT230_ALERT_2_C Hirshfeld Test Diff for S1A - C18B .. 6.54 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C18A - C16B .. 6.53 su PLAT230_ALERT_2_C Hirshfeld Test Diff for C16B - C18B .. 6.53 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C16A PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for S1B PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C15A PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C15B PLAT301_ALERT_3_C Main Residue Disorder ......................... 21.00 Perc. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C13 - C14 ... 1.36 Ang.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 29.05 From the CIF: _reflns_number_total 3018 Count of symmetry unique reflns 1908 Completeness (_total/calc) 158.18% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1110 Fraction of Friedel pairs measured 0.582 Are heavy atom types Z>Si present yes PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 4
0 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 12 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

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.

Related literature top

For a related structure, see: Fave et al., 2004.

For related literature, see: Allen (2002); Lukeš et al. (2003); Mullen & Wegner (1998).

Experimental top

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 top

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).

Structure description top

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.

For a related structure, see: Fave et al., 2004.

For related literature, see: Allen (2002); Lukeš et al. (2003); Mullen & Wegner (1998).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (Oxford Diffraction, 2006); 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).

Figures top
[Figure 1] 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.
2-(9H-Fluoren-9-ylidenemethyl)thiophene top
Crystal data top
C18H12SF(000) = 2176
Mr = 260.34Dx = 1.333 Mg m3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 4617 reflections
a = 20.757 (4) Åθ = 3.7–29.1°
b = 44.434 (9) ŵ = 0.23 mm1
c = 5.6260 (11) ÅT = 100 K
V = 5189.0 (18) Å3Block, yellow
Z = 160.57 × 0.13 × 0.08 mm
Data collection top
Oxford Diffraction Gemini R CCD
diffractometer
3018 independent reflections
Radiation source: fine-focus sealed tube1903 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
Rotation method data acquisition using ω and φ scansθmax = 29.1°, θmin = 3.8°
Absorption correction: analytical
(Clark & Reid, 1995)
h = 2725
Tmin = 0.938, Tmax = 0.985k = 5958
11725 measured reflectionsl = 77
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.090 w = 1/[σ2(Fo2) + (0.0485P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max < 0.001
3018 reflectionsΔρmax = 0.15 e Å3
180 parametersΔρmin = 0.17 e Å3
4 restraintsAbsolute structure: Flack (1983), 1110 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.07 (8)
Crystal data top
C18H12SV = 5189.0 (18) Å3
Mr = 260.34Z = 16
Orthorhombic, Fdd2Mo Kα radiation
a = 20.757 (4) ŵ = 0.23 mm1
b = 44.434 (9) ÅT = 100 K
c = 5.6260 (11) Å0.57 × 0.13 × 0.08 mm
Data collection top
Oxford Diffraction Gemini R CCD
diffractometer
3018 independent reflections
Absorption correction: analytical
(Clark & Reid, 1995)
1903 reflections with I > 2σ(I)
Tmin = 0.938, Tmax = 0.985Rint = 0.029
11725 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.090Δρmax = 0.15 e Å3
S = 0.99Δρmin = 0.17 e Å3
3018 reflectionsAbsolute structure: Flack (1983), 1110 Friedel pairs
180 parametersAbsolute structure parameter: 0.07 (8)
4 restraints
Special details top

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) top
xyzUiso*/UeqOcc. (<1)
C10.35040 (9)0.03543 (4)0.1480 (3)0.0504 (5)
C20.40287 (10)0.01668 (4)0.1107 (4)0.0605 (6)
H2A0.42980.01940.02410.073*
C30.41552 (10)0.00616 (5)0.2727 (4)0.0656 (6)
H3A0.45160.01890.24750.079*
C40.37726 (11)0.01069 (5)0.4680 (4)0.0640 (6)
H4A0.38760.02620.57810.077*
C50.32362 (10)0.00724 (4)0.5052 (4)0.0594 (5)
H5A0.29650.00400.63870.071*
C60.31044 (9)0.02985 (4)0.3442 (3)0.0490 (5)
C70.25624 (9)0.05093 (4)0.3394 (3)0.0493 (5)
C80.20399 (10)0.05396 (5)0.4884 (4)0.0607 (5)
H8A0.19940.04130.62370.073*
C90.15827 (11)0.07574 (5)0.4373 (4)0.0670 (6)
H9A0.12190.07800.53800.080*
C100.16522 (10)0.09415 (5)0.2405 (4)0.0658 (6)
H10A0.13340.10900.20790.079*
C110.21746 (10)0.09134 (5)0.0913 (4)0.0608 (5)
H11A0.22210.10430.04190.073*
C120.26339 (9)0.06932 (4)0.1380 (3)0.0490 (5)
C130.32372 (9)0.06148 (4)0.0145 (3)0.0490 (5)
C140.34399 (9)0.07789 (4)0.1761 (3)0.0518 (5)
H14A0.31250.09210.22560.062*
C15A0.40114 (9)0.07913 (4)0.3214 (3)0.0513 (5)0.900 (3)
C18A0.50774 (12)0.07874 (5)0.5125 (5)0.0731 (7)0.900 (3)
H18A0.55130.07590.55920.088*0.900 (3)
C17A0.46607 (12)0.09565 (5)0.6332 (4)0.0670 (6)0.900 (3)
H17A0.47670.10580.77670.080*0.900 (3)
C16A0.4056 (4)0.0970 (4)0.529 (3)0.0747 (14)0.900 (3)
H16A0.37100.10870.59000.090*0.900 (3)
S1A0.47511 (8)0.06280 (3)0.26734 (16)0.0755 (3)0.900 (3)
C15B0.40114 (9)0.07913 (4)0.3214 (3)0.0513 (5)0.100 (3)
C17B0.46607 (12)0.09565 (5)0.6332 (4)0.0670 (6)0.100 (3)
H17B0.47810.10580.77500.080*0.100 (3)
C18B0.50774 (12)0.07874 (5)0.5125 (5)0.0731 (7)0.100 (3)
H18B0.55120.07580.56020.088*0.100 (3)
C16B0.481 (3)0.0659 (10)0.311 (4)0.0755 (3)0.100 (3)
H16B0.50130.05320.19600.091*0.100 (3)
S1B0.3980 (11)0.0978 (10)0.532 (7)0.0747 (14)0.100 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0532 (11)0.0451 (11)0.0528 (11)0.0072 (9)0.0047 (9)0.0017 (9)
C20.0557 (12)0.0503 (12)0.0754 (13)0.0021 (10)0.0032 (11)0.0117 (11)
C30.0575 (12)0.0517 (12)0.0874 (16)0.0001 (10)0.0055 (12)0.0126 (12)
C40.0699 (14)0.0503 (13)0.0717 (13)0.0051 (11)0.0093 (13)0.0153 (12)
C50.0684 (13)0.0544 (12)0.0555 (11)0.0128 (10)0.0014 (11)0.0072 (11)
C60.0570 (11)0.0428 (11)0.0473 (10)0.0082 (9)0.0039 (10)0.0004 (9)
C70.0542 (11)0.0438 (11)0.0500 (11)0.0054 (9)0.0035 (9)0.0041 (10)
C80.0657 (13)0.0608 (13)0.0557 (10)0.0042 (11)0.0049 (12)0.0017 (11)
C90.0649 (14)0.0688 (15)0.0673 (15)0.0031 (11)0.0130 (11)0.0128 (12)
C100.0643 (13)0.0580 (13)0.0750 (14)0.0076 (10)0.0009 (12)0.0077 (13)
C110.0671 (13)0.0519 (12)0.0634 (12)0.0033 (10)0.0028 (12)0.0026 (11)
C120.0520 (11)0.0468 (10)0.0483 (11)0.0047 (9)0.0057 (8)0.0018 (9)
C130.0528 (10)0.0461 (10)0.0482 (11)0.0072 (9)0.0042 (9)0.0000 (9)
C140.0555 (11)0.0487 (11)0.0513 (11)0.0028 (9)0.0087 (9)0.0005 (9)
C15A0.0598 (12)0.0461 (11)0.0480 (11)0.0100 (9)0.0005 (9)0.0023 (9)
C18A0.0757 (15)0.0666 (15)0.0771 (14)0.0061 (12)0.0193 (14)0.0019 (14)
C17A0.0865 (16)0.0614 (14)0.0531 (12)0.0118 (13)0.0108 (12)0.0052 (12)
C16A0.082 (3)0.0744 (16)0.0680 (12)0.022 (2)0.005 (2)0.0022 (11)
S1A0.0667 (6)0.0868 (6)0.0731 (5)0.0098 (4)0.0143 (4)0.0252 (5)
C15B0.0598 (12)0.0461 (11)0.0480 (11)0.0100 (9)0.0005 (9)0.0023 (9)
C17B0.0865 (16)0.0614 (14)0.0531 (12)0.0118 (13)0.0108 (12)0.0052 (12)
C18B0.0757 (15)0.0666 (15)0.0771 (14)0.0061 (12)0.0193 (14)0.0019 (14)
C16B0.0667 (6)0.0868 (6)0.0731 (5)0.0098 (4)0.0143 (4)0.0252 (5)
S1B0.082 (3)0.0744 (16)0.0680 (12)0.022 (2)0.005 (2)0.0022 (11)
Geometric parameters (Å, º) top
C1—C21.387 (3)C10—C111.377 (3)
C1—C61.403 (3)C10—H10A0.9500
C1—C131.487 (3)C11—C121.391 (3)
C2—C31.389 (3)C11—H11A0.9500
C2—H2A0.9500C12—C131.474 (3)
C3—C41.371 (3)C13—C141.363 (3)
C3—H3A0.9500C14—C15A1.442 (3)
C4—C51.385 (3)C14—H14A0.9500
C4—H4A0.9500C15A—C16A1.416 (19)
C5—C61.380 (3)C15A—S1A1.725 (3)
C5—H5A0.9500C18A—C17A1.332 (3)
C6—C71.464 (3)C18A—S1A1.692 (3)
C7—C81.377 (3)C18A—H18A0.9500
C7—C121.405 (3)C17A—C16A1.388 (3)
C8—C91.386 (3)C17A—H17A0.9500
C8—H8A0.9500C16A—H16A0.9500
C9—C101.384 (3)C16B—H16B0.9500
C9—H9A0.9500
C2—C1—C6118.53 (18)C11—C10—H10A119.5
C2—C1—C13133.10 (18)C9—C10—H10A119.5
C6—C1—C13108.35 (17)C10—C11—C12119.2 (2)
C1—C2—C3119.2 (2)C10—C11—H11A120.4
C1—C2—H2A120.4C12—C11—H11A120.4
C3—C2—H2A120.4C11—C12—C7119.26 (19)
C4—C3—C2121.6 (2)C11—C12—C13131.25 (18)
C4—C3—H3A119.2C7—C12—C13109.45 (17)
C2—C3—H3A119.2C14—C13—C12120.45 (17)
C3—C4—C5120.2 (2)C14—C13—C1134.33 (19)
C3—C4—H4A119.9C12—C13—C1105.19 (16)
C5—C4—H4A119.9C13—C14—C15A136.09 (18)
C6—C5—C4118.6 (2)C13—C14—H14A112.0
C6—C5—H5A120.7C15A—C14—H14A112.0
C4—C5—H5A120.7C16A—C15A—C14122.8 (4)
C5—C6—C1121.84 (18)C16A—C15A—S1A108.9 (4)
C5—C6—C7129.06 (17)C14—C15A—S1A128.03 (14)
C1—C6—C7109.09 (16)C17A—C18A—S1A113.1 (2)
C8—C7—C12121.16 (18)C17A—C18A—H18A123.5
C8—C7—C6131.03 (19)S1A—C18A—H18A123.5
C12—C7—C6107.78 (17)C18A—C17A—C16A113.4 (9)
C7—C8—C9118.8 (2)C18A—C17A—H17A123.3
C7—C8—H8A120.6C16A—C17A—H17A123.3
C9—C8—H8A120.6C17A—C16A—C15A112.5 (12)
C10—C9—C8120.5 (2)C17A—C16A—H16A123.8
C10—C9—H9A119.8C15A—C16A—H16A123.8
C8—C9—H9A119.8C18A—S1A—C15A92.08 (13)
C11—C10—C9121.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···S1A0.952.553.311 (4)139

Experimental details

Crystal data
Chemical formulaC18H12S
Mr260.34
Crystal system, space groupOrthorhombic, Fdd2
Temperature (K)100
a, b, c (Å)20.757 (4), 44.434 (9), 5.6260 (11)
V3)5189.0 (18)
Z16
Radiation typeMo Kα
µ (mm1)0.23
Crystal size (mm)0.57 × 0.13 × 0.08
Data collection
DiffractometerOxford Diffraction Gemini R CCD
Absorption correctionAnalytical
(Clark & Reid, 1995)
Tmin, Tmax0.938, 0.985
No. of measured, independent and
observed [I > 2σ(I)] reflections
11725, 3018, 1903
Rint0.029
(sin θ/λ)max1)0.683
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.090, 0.99
No. of reflections3018
No. of parameters180
No. of restraints4
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.15, 0.17
Absolute structureFlack (1983), 1110 Friedel pairs
Absolute structure parameter0.07 (8)

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1998), enCIFer (Allen et al., 2004).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···S1A0.952.553.311 (4)138.51
 

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