supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, o3961    [ doi:10.1107/S1600536807041578 ]

3,3',4,4'-Tetrabutyl-5,5'-(biphenyl-4,4'-diyldiethynyl)bis(thiophene-2-carbonitrile)

L. Liu, W. Xu, X.-W. Xiao and D.-B. Zhu

Abstract top

The molecule of the title compound, C42H44N2S2, is centrosymmetric. Thus, an asymmetric unit comprises half of the molecule. The torsion angle of the C-C[triple bond]C-C backbone is -165.6 (4)°. The crystal packing is dominated by van der Waals interactions.

Comment top

By developing new techniques to fabricate miniature components, and to fit more components into each cm 2 of silicon, engineers have driven the speed and capabilities of computing at a predictably fast pace. But the reduction in size of components, and thus increase in speed, can only continue for some finite time. New processes are under development in order to extend the useful functionality of silicon integrated circuits (Carroll et al., 2002).

Linear, π-conjugated molecules have attracted great attention due to their potential in molecular scale electronic devices (Bloor, 1995; Bumm et al., 1996). Molecular wires typically consist of two electroactive functional groups linked by an extended π-electron network. Rainer E. Martin synthesized a series of monodisperse Me3Si -endcapped poly(triacetylene) oligomers (Martin et al., 1997; Martin et al., 1999). Here, the synthesis and crystal structures of 4,4'-dicyano- (3,4-dibutylthiophenylethynyl)biphenyl (I) are presented.

The molecular structure of the title compound (Fig. 1) is centrosymmetric. Thus, an asymmetric unit comprises a half on the molecule. The inversion centre is located in the middle of C3—C3i bond. The two phenyl rings and carbon triple bonds are coplanar. The torsion angle of C9—C8—C7—C6 is −165.6 (4)° whereas the diphenyl moiety is linear due to an inversion symmetry of the molecule. The crystal packing (Fig. 2) is dominated by van der Waals interactions.

Related literature top

For related literature, see: Bloor (1995); Bumm et al. (1996); Carroll & Gorman (2002); Liu et al. (2006); Martin et al. (1997, 1999).

Experimental top

The synthesis of the title compound was performed as described by Liu et al. (2006).

Colourless plate-like crystals of 4,4'-dicyano-(3,4-dibutyl-thienyl ethynyl) biphenyl were grown from ethanol /hexane mixture by slow evaporation of the solution.

Refinement top

Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 1998); software used

to prepare material for publication: SHELXTL (Siemens, 1994).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1994 or Bruker, 1998) or XP (Bruker, 1998)?; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and displacement ellipsoids at the 50% probability. To generate the molecule symmetry code −x, −y, −z + 2 is applied.
[Figure 2] Fig. 2. The crystal packing along a axis of the title compound.
3,3',4,4'-Tetrabutyl-5,5'-(biphenyl-4,4'-diyldiethynyl)bis(thiophene-2-\ carbonitrile) top
Crystal data top
C42H44N2S2V = 922.3 (3) Å3
Mr = 640.91Z = 1
Triclinic, P1F(000) = 342
a = 8.1428 (16) ÅDx = 1.154 Mg m−3
b = 9.1856 (18) ÅMo Kα radiation, λ = 0.71073 Å
c = 13.606 (3) ŵ = 0.18 mm−1
α = 90.37 (3)°T = 293 K
β = 100.53 (3)°Plate, colourless
γ = 112.32 (3)°0.41 × 0.39 × 0.28 mm
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		4080 independent reflections
Radiation source: fine-focus sealed tube3287 reflections with I > 2σ(I)
graphiteRint = 0.029
Detector resolution: 0.76 pixels mm-1θmax = 27.5°, θmin = 1.5°
Oscillation scansh = −9→10
Absorption correction: empirical (using intensity measurements)
(ABSCOR; Higashi, 1995)		k = −9→11
Tmin = 0.879, Tmax = 0.996l = −17→17
5834 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.071Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.235H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.1503P)2 + 0.3412P]
where P = (Fo2 + 2Fc2)/3
4080 reflections(Δ/σ)max < 0.001
208 parametersΔρmax = 0.81 e Å−3
0 restraintsΔρmin = −0.38 e Å−3
Crystal data top
C42H44N2S2γ = 112.32 (3)°
Mr = 640.91V = 922.3 (3) Å3
Triclinic, P1Z = 1
a = 8.1428 (16) ÅMo Kα radiation
b = 9.1856 (18) ŵ = 0.18 mm−1
c = 13.606 (3) ÅT = 293 K
α = 90.37 (3)°0.41 × 0.39 × 0.28 mm
β = 100.53 (3)°
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		4080 independent reflections
Absorption correction: empirical (using intensity measurements)
(ABSCOR; Higashi, 1995)		3287 reflections with I > 2σ(I)
Tmin = 0.879, Tmax = 0.996Rint = 0.029
5834 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.071H-atom parameters constrained
wR(F2) = 0.235Δρmax = 0.81 e Å−3
S = 1.01Δρmin = −0.38 e Å−3
4080 reflectionsAbsolute structure: ?
208 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

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*/Ueq
S10.28848 (9)0.32421 (9)0.44787 (5)0.0608 (3)
C10.1734 (4)0.2078 (4)0.8390 (2)0.0766 (9)
H1A0.27730.29200.83080.092*
N10.4301 (5)0.4639 (4)0.2102 (3)0.1016 (11)
C20.1583 (4)0.1546 (4)0.9336 (2)0.0752 (9)
H2A0.25240.20490.98780.090*
C30.0075 (3)0.0290 (3)0.94934 (16)0.0469 (5)
C4−0.1306 (4)−0.0409 (3)0.86606 (19)0.0639 (7)
H4A−0.2353−0.12450.87400.077*
C5−0.1156 (4)0.0112 (3)0.77223 (19)0.0662 (7)
H5A−0.2095−0.03930.71790.079*
C60.0349 (4)0.1361 (3)0.75692 (17)0.0533 (6)
C70.0492 (4)0.1910 (3)0.65898 (19)0.0574 (6)
C80.0589 (4)0.2360 (3)0.57725 (18)0.0556 (6)
C90.0843 (3)0.2910 (3)0.48107 (17)0.0506 (5)
C10−0.0335 (3)0.3280 (3)0.40904 (17)0.0492 (5)
C110.0437 (4)0.3854 (3)0.32413 (18)0.0534 (6)
C120.2171 (4)0.3890 (3)0.3356 (2)0.0589 (6)
C130.3348 (5)0.4322 (4)0.2656 (2)0.0717 (8)
C14−0.2209 (4)0.3068 (3)0.4213 (2)0.0589 (6)
H14A−0.24540.39700.39700.071*
H14B−0.22420.30580.49220.071*
C15−0.0488 (5)0.4360 (4)0.2334 (2)0.0686 (8)
H15A0.03660.53350.21510.082*
H15B−0.14780.45830.25070.082*
C16−0.3690 (4)0.1584 (4)0.3671 (3)0.0848 (10)
H16A−0.48200.15040.38490.102*
H16B−0.38090.16990.29570.102*
C17−0.1229 (5)0.3166 (5)0.1432 (2)0.0803 (9)
H17A−0.19590.21490.16320.096*
H17B−0.02270.30540.11930.096*
C18−0.3470 (6)0.0111 (5)0.3857 (4)0.1018 (13)
H18A−0.32990.00150.45740.122*
H18B−0.23690.01700.36500.122*
C19−0.2385 (7)0.3634 (6)0.0574 (3)0.1009 (13)
H19A−0.34020.37180.08100.121*
H19B−0.16630.46680.03920.121*
C20−0.5024 (6)−0.1393 (4)0.3335 (4)0.0994 (12)
H20A−0.4765−0.22980.35320.149*
H20B−0.5152−0.13570.26210.149*
H20C−0.6130−0.14680.35260.149*
C21−0.3088 (8)0.2507 (7)−0.0336 (3)0.1312 (19)
H21A−0.38060.2867−0.08380.197*
H21B−0.38230.1483−0.01670.197*
H21C−0.20910.2443−0.05900.197*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0507 (4)0.0685 (5)0.0586 (4)0.0192 (3)0.0086 (3)0.0062 (3)
C10.0565 (15)0.092 (2)0.0554 (15)0.0035 (15)0.0041 (12)0.0216 (14)
N10.109 (3)0.090 (2)0.111 (2)0.0240 (19)0.067 (2)0.0237 (18)
C20.0547 (14)0.092 (2)0.0499 (14)0.0031 (14)−0.0033 (11)0.0171 (14)
C30.0491 (12)0.0484 (12)0.0435 (11)0.0205 (10)0.0063 (9)0.0037 (9)
C40.0622 (15)0.0614 (16)0.0479 (13)0.0051 (12)0.0037 (11)0.0033 (11)
C50.0703 (17)0.0661 (16)0.0439 (13)0.0121 (13)−0.0013 (11)−0.0005 (11)
C60.0623 (14)0.0603 (14)0.0433 (12)0.0305 (12)0.0100 (10)0.0085 (10)
C70.0645 (15)0.0634 (15)0.0490 (13)0.0300 (13)0.0115 (11)0.0066 (11)
C80.0613 (14)0.0601 (14)0.0454 (12)0.0242 (12)0.0089 (10)0.0054 (10)
C90.0520 (12)0.0518 (12)0.0437 (11)0.0157 (10)0.0092 (9)0.0033 (9)
C100.0549 (13)0.0455 (12)0.0443 (11)0.0168 (10)0.0086 (9)0.0014 (9)
C110.0645 (14)0.0464 (12)0.0472 (12)0.0188 (11)0.0119 (10)0.0059 (9)
C120.0639 (15)0.0546 (14)0.0547 (14)0.0160 (12)0.0189 (12)0.0096 (11)
C130.0767 (19)0.0607 (16)0.0757 (19)0.0164 (14)0.0325 (16)0.0100 (13)
C140.0606 (15)0.0583 (14)0.0621 (15)0.0266 (12)0.0149 (12)0.0025 (11)
C150.094 (2)0.0677 (17)0.0520 (14)0.0403 (16)0.0142 (14)0.0149 (12)
C160.0577 (17)0.082 (2)0.110 (3)0.0246 (16)0.0124 (17)−0.0179 (19)
C170.101 (2)0.092 (2)0.0537 (16)0.050 (2)0.0030 (15)0.0039 (15)
C180.080 (2)0.074 (2)0.148 (4)0.028 (2)0.016 (2)−0.006 (2)
C190.122 (3)0.133 (4)0.064 (2)0.075 (3)0.001 (2)0.004 (2)
C200.092 (3)0.067 (2)0.122 (3)0.0202 (19)0.004 (2)−0.008 (2)
C210.151 (5)0.169 (5)0.080 (3)0.087 (4)−0.016 (3)−0.010 (3)
Geometric parameters (Å, °) top
S1—C91.718 (3)C14—H14A0.9700
S1—C121.725 (3)C14—H14B0.9700
C1—C61.386 (4)C15—C171.511 (4)
C1—C21.389 (4)C15—H15A0.9700
C1—H1A0.9300C15—H15B0.9700
N1—C131.140 (4)C16—C181.448 (5)
C2—C31.381 (4)C16—H16A0.9700
C2—H2A0.9300C16—H16B0.9700
C3—C41.392 (4)C17—C191.531 (5)
C3—C3i1.490 (4)C17—H17A0.9700
C4—C51.376 (4)C17—H17B0.9700
C4—H4A0.9300C18—C201.532 (6)
C5—C61.375 (4)C18—H18A0.9700
C5—H5A0.9300C18—H18B0.9700
C6—C71.437 (3)C19—C211.484 (6)
C7—C81.195 (4)C19—H19A0.9700
C8—C91.428 (3)C19—H19B0.9700
C9—C101.380 (4)C20—H20A0.9600
C10—C111.425 (3)C20—H20B0.9600
C10—C141.504 (4)C20—H20C0.9600
C11—C121.380 (4)C21—H21A0.9600
C11—C151.497 (4)C21—H21B0.9600
C12—C131.425 (4)C21—H21C0.9600
C14—C161.506 (4)
C9—S1—C1290.36 (13)C11—C15—H15A108.6
C6—C1—C2120.4 (3)C17—C15—H15A108.6
C6—C1—H1A119.8C11—C15—H15B108.6
C2—C1—H1A119.8C17—C15—H15B108.6
C3—C2—C1121.9 (3)H15A—C15—H15B107.6
C3—C2—H2A119.1C18—C16—C14117.0 (3)
C1—C2—H2A119.1C18—C16—H16A108.0
C2—C3—C4116.9 (2)C14—C16—H16A108.0
C2—C3—C3i121.7 (3)C18—C16—H16B108.0
C4—C3—C3i121.4 (3)C14—C16—H16B108.0
C5—C4—C3121.4 (3)H16A—C16—H16B107.3
C5—C4—H4A119.3C15—C17—C19112.6 (3)
C3—C4—H4A119.3C15—C17—H17A109.1
C6—C5—C4121.5 (3)C19—C17—H17A109.1
C6—C5—H5A119.2C15—C17—H17B109.1
C4—C5—H5A119.2C19—C17—H17B109.1
C5—C6—C1117.9 (2)H17A—C17—H17B107.8
C5—C6—C7121.3 (2)C16—C18—C20116.4 (4)
C1—C6—C7120.8 (3)C16—C18—H18A108.2
C8—C7—C6179.2 (3)C20—C18—H18A108.2
C7—C8—C9175.7 (3)C16—C18—H18B108.2
C10—C9—C8128.5 (2)C20—C18—H18B108.2
C10—C9—S1113.10 (18)H18A—C18—H18B107.4
C8—C9—S1118.34 (19)C21—C19—C17114.0 (4)
C9—C10—C11112.0 (2)C21—C19—H19A108.8
C9—C10—C14122.5 (2)C17—C19—H19A108.8
C11—C10—C14125.5 (2)C21—C19—H19B108.8
C12—C11—C10111.3 (2)C17—C19—H19B108.8
C12—C11—C15123.5 (2)H19A—C19—H19B107.7
C10—C11—C15125.2 (3)C18—C20—H20A109.5
C11—C12—C13128.0 (3)C18—C20—H20B109.5
C11—C12—S1113.28 (19)H20A—C20—H20B109.5
C13—C12—S1118.7 (2)C18—C20—H20C109.5
N1—C13—C12178.3 (4)H20A—C20—H20C109.5
C10—C14—C16114.4 (2)H20B—C20—H20C109.5
C10—C14—H14A108.7C19—C21—H21A109.5
C16—C14—H14A108.7C19—C21—H21B109.5
C10—C14—H14B108.7H21A—C21—H21B109.5
C16—C14—H14B108.7C19—C21—H21C109.5
H14A—C14—H14B107.6H21A—C21—H21C109.5
C11—C15—C17114.6 (2)H21B—C21—H21C109.5
C12—C11—C10—C90.1 (3)C1—C2—C3—C4−0.9 (5)
C12—S1—C9—C100.0 (3)C5—C4—C3—C21.1 (6)
C10—C11—C12—S1−0.1 (1)C5—C6—C1—C2−0.4 (5)
C11—C12—S1—C90.0 (5)C12—C11—C15—C1777.9 (4)
C11—C10—C9—S1−0.1 (3)C11—C15—C17—C19172.0 (7)
C11—C10—C9—C8177.5 (5)C15—C17—C19—C21178.2 (5)
C12—S1—C9—C8−177.8 (8)C10—C11—C15—C17−102.1 (3)
C7—C6—C5—C4−179.4 (1)C11—C10—C14—C1679.8 (7)
C7—C6—C1—C2179.6 (8)C9—C10—C14—C16−99.4 (5)
C6—C5—C4—C3−1.1 (5)C10—C14—C16—C1852.3 (7)
C6—C1—C2—C30.5 (7)C14—C16—C18—C20177.5 (2)
C4—C5—C6—C10.7 (2)C4—C3—C3—C490.00 (3)
Symmetry codes: (i) −x, −y, −z+2.
Acknowledgements top

This work was supported financially by the National Natural Science Foundation of China (grant Nos. 20421101, 20572113) and the State Basic Research Development Program (grant No. G2000077505).

references
References top

Bloor, D. (1995). Introduction to Molecular Electronics, edited by M. C. Petty, M. R. Bryce & D. Bloor, pp. 1–28. London: Edward Arnold.

Bruker (1998). XP and SHEXLXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Bumm, L. A., Arnold, J. J., Cygan, M. T., Dunbar, T. D., Burgin, T. P., Jones, L. II, Allara, D. L., Tour, J. M. & Weiss, P. S. (1996). Science, pp. 1705–2707.

Carroll, R. L. & Gorman, C. B. (2002). Angew. Chem. Int. Ed. 41, 4378–4400.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Liu, L., Liu, Z., Xu, W., Xu, H., Zhang, D. & Zhu, D. (2006). Thin Solid Films, 515, 2596–2601.

Martin, R. E., Gubler, U., Boudon, C., Gramlich, V., Bosshard, C., Gisselbrecht, J. P., Gunter, P., Gross, M. & Diederich, F. (1997). Chem. Eur. J. pp. 1505–1512.

Martin, R. E., Mader, T. & Diederich, F. (1999). Angew. Chem. Int. Ed. 38, 817–821.

Rigaku (2001). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Siemens (1994). SHELXTL. Release 5.03. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.