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Acta Cryst. (2007). E63, o3054-o3055    [ doi:10.1107/S1600536807025366 ]

(Z)-2-Phenyl-3-(2,2':5',2''-terthiophen-3'-yl)acrylonitrile

P. Wagner, D. L. Officer and M. Kubicki

Abstract top

In the crystal structure of the title compound, C21H13NS3, one of the terminal thiophene rings is disordered in approximately a 3:1 ratio of components, and the disorder is of the flip type. The terthiophene units are far from coplanarity, in contrast to terthiophene itself. The conformation might be described, for the unit of greater occupancy, as quasi-cis [the S-C-C-S torsion angle is 41.1 (5)°] quasi-trans [the S-C-C-S torsion angle is -140.1 (4)°], and for the less-occupied part as quasi-cis-quasi-cis [35.7 (6)°]. The dihedral angle between the terminal ring planes is as high as 71.7 (2)°. The central C-C=C-C group is almost planar [maximum deviation of 0.027 (3) Å] and it is approximately equally twisted with respect to both the central thiophene and the phenyl ring planes [26.5 (4) and 23.5 (7)°, respectively]. The crystal packing is determined by van der Waals interactions, and some weak C-H...N and C-H...[pi] relatively short directional contacts.

Comment top

Oligo- and polythiophenes, potentially applicable as sollar cells, light-emitting diodes or NLO materials (Skotheim & Reynolds, 2007) are widely studied due to their good chemical stability in both oxidized and reduced states, and to relatively easy functionalization of the monomers whether thiophene, bithiophene, or terthiophene (for example: Roncali, 1999; Grant & Officer, 2005 and references therein).

Recently we have proposed an alternative approach to the formation of regioregular styryl-functionalized oligo- and polythiophenes (for example, Collis et al., 2003; Grant & Officer, 2005). We have demonstrated that the styryl functionality can control oligomer regioregularity and provides advantages in some applications. However styrylterthiophenes largely form dimers on oxidative polymerization as a result of "polaron trapping" (Clarke et al., 2007).

There is a flip-disorder of one of the terminal thiophene rings. The disorder is connected with two statistically distributed orientations of the thiophene sulfur atom. In practice that means that there are two molecules in which the thiophene rings are rotated by 180° approximately along the line that bisects the S—C—C angle. These two orientations are not equivalent, but they are distributed approximately in 3:1 proportion. The conformation of the molecule of greater occupancy might be described as quasi-trans-quasi-cis, while that of smaller occupancy is quasi-cis-quasi-cis. A disorder of this kind is often observed in the structures of simple thiophene and terthiophene derivatives with one substituent; for example in similar (E)-3'-(2-(4-cyanophenyl)ethenyl)-[2,2':5',2'']terthiophene (Collis et al., 2003) or in 3-(2-(anthracen-9-yl)ethenyl)-thiophene (Wagner et al., 2006).

The terthiophene rings are approximately planar (maximum deviation is 0.020 (6) Å), but the dihedral angles between their planes are large (for instance, between the terminal rings it is 71.7 (2)°). Also the planar (within 0.012 (3) Å) phenyl ring is inclined by 49.9 (2)° with respect to the central thiophene ring. In the crystal structure the van der Waals forces seem to determine the packing. Some weak specific C13—H13···N19i and C25—H25···π (Cg1ii) (Cg1 is the centroid of C11···C15 thiophene ring, symmetry codes as in Table 1) directional interactions also might be of some importance.

Related literature top

Similar flip-type disorder was observed in other 3'-arylvinyl derivatives of terthiophene [without additional substituents at the vinyl group, e.g. Wagner et al. (2007)], or in simple thiophene derivatives (e.g. Sonar et al., 2004, 2005; Wagner et al., 2006). For related literature, see: Clarke et al. (2007); Collis et al. (2003); Grant & Officer (2005); Roncali (1999); Skotheim & Reynolds (2007).

Refinement top

Hydrogen atoms were placed at calculated positions and refined as 'riding model' with isotropic thermal parameters set at 1.2 (1.3 for methyl groups) times the Ueq values of appropriate carrier atoms. In the disordered part, the carbon atoms of the were constrained to have the same components of the displacement tensor as the sulfur atoms occupying the same site. Weak restraints were also applied to the geometry of disordered fragment.

Computing details top

Data collection: XSCANS (Bruker, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level for non H-atoms (Siemens, 1989)
(2Z)-2-Phenyl-3-(2,2':5',2''-terthiophen-3'-yl)acrylonitrile top
Crystal data top
C21H13NS3F000 = 776
Mr = 375.50Dx = 1.432 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2212 reflections
a = 9.167 (1) Åθ = 5–15º
b = 19.564 (2) ŵ = 0.43 mm−1
c = 10.424 (1) ÅT = 173 (1) K
β = 111.30 (1)ºBlock, yellow
V = 1741.8 (3) Å30.26 × 0.2 × 0.16 mm
Z = 4
Data collection top
Bruker P4 CCD
diffractometer		1861 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.149
Monochromator: graphiteθmax = 25.0º
T = 173(1) Kθmin = 2.1º
ω scansh = −10→10
Absorption correction: nonek = −23→22
10129 measured reflectionsl = −11→12
3054 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.066  w = 1/[σ2(Fo2) + (0.05P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.153(Δ/σ)max < 0.001
S = 1.02Δρmax = 0.56 e Å−3
3054 reflectionsΔρmin = −0.68 e Å−3
233 parametersExtinction correction: none
51 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Crystal data top
C21H13NS3V = 1741.8 (3) Å3
Mr = 375.50Z = 4
Monoclinic, P21/cMo Kα
a = 9.167 (1) ŵ = 0.43 mm−1
b = 19.564 (2) ÅT = 173 (1) K
c = 10.424 (1) Å0.26 × 0.2 × 0.16 mm
β = 111.30 (1)º
Data collection top
Bruker P4 CCD
diffractometer		3054 independent reflections
Absorption correction: none1861 reflections with I > 2σ(I)
10129 measured reflectionsRint = 0.149
Refinement top
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.153Δρmax = 0.56 e Å−3
S = 1.02Δρmin = −0.68 e Å−3
3054 reflectionsAbsolute structure: ?
233 parametersFlack parameter: ?
51 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 > 2sigma(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)
S10.56931 (14)0.14221 (6)−0.00033 (13)0.0210 (3)
C20.6725 (5)0.0783 (2)0.1084 (5)0.0159 (11)
C30.7043 (6)0.0252 (2)0.0376 (5)0.0183 (11)
C40.6420 (5)0.0369 (2)−0.1078 (5)0.0178 (11)
H40.65220.0058−0.17160.021*
C50.5666 (5)0.0978 (2)−0.1438 (5)0.0185 (11)
C60.7141 (5)0.0857 (2)0.2557 (5)0.0180 (11)
S70.58362 (16)0.11909 (7)0.32299 (13)0.0260 (4)
C80.7152 (6)0.1126 (3)0.4875 (5)0.0260 (13)
H80.69520.12620.56500.031*
C90.8511 (6)0.0855 (3)0.4913 (5)0.0270 (13)
H90.93500.07750.57290.032*
C100.8555 (5)0.0704 (2)0.3611 (4)0.0158 (11)
H100.94230.05240.34690.019*
C110.4806 (5)0.1228 (2)−0.2812 (5)0.0201 (11)
S120.3782 (5)0.06990 (10)−0.4104 (3)0.0205 (7)0.725 (5)
C120.379 (5)0.0865 (15)−0.413 (3)0.0205 (7)0.275 (5)
H120.37360.0391−0.41380.025*0.275 (5)
C130.3084 (6)0.1337 (3)−0.5189 (6)0.0325 (14)
H130.24110.1261−0.60910.039*
C140.3516 (6)0.1956 (3)−0.4733 (5)0.0314 (14)
H140.31980.2362−0.52180.038*
C150.4584 (14)0.1880 (5)−0.3325 (10)0.0231 (12)0.725 (5)
H150.50910.2253−0.27980.028*0.725 (5)
S150.4713 (9)0.2068 (2)−0.3123 (6)0.0231 (12)0.275 (5)
C160.7830 (5)−0.0363 (2)0.1054 (5)0.0192 (11)
H160.7778−0.04520.19130.023*
C170.8621 (5)−0.0818 (2)0.0607 (5)0.0171 (11)
C180.8859 (5)−0.0716 (2)−0.0653 (5)0.0172 (11)
N190.9073 (5)−0.0643 (2)−0.1664 (4)0.0265 (11)
C200.9287 (5)−0.1459 (2)0.1335 (5)0.0175 (11)
C211.0512 (6)−0.1787 (3)0.1111 (5)0.0223 (12)
H211.0948−0.15940.05180.027*
C221.1089 (6)−0.2397 (3)0.1758 (5)0.0266 (13)
H221.1898−0.26180.15860.032*
C231.0471 (6)−0.2681 (3)0.2657 (5)0.0260 (13)
H231.0861−0.30920.30950.031*
C240.9279 (5)−0.2354 (3)0.2906 (5)0.0238 (12)
H240.8860−0.25440.35150.029*
C250.8696 (5)−0.1743 (2)0.2257 (5)0.0196 (11)
H250.7898−0.15210.24430.024*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0144 (7)0.0187 (7)0.0234 (7)0.0031 (6)−0.0008 (5)−0.0007 (5)
C20.0102 (18)0.0141 (18)0.0197 (17)0.0004 (15)0.0008 (14)0.0010 (14)
C30.0141 (19)0.0172 (18)0.0217 (18)−0.0004 (15)0.0043 (15)−0.0006 (15)
C40.009 (3)0.020 (3)0.022 (3)−0.003 (2)0.002 (2)−0.007 (2)
C50.010 (3)0.023 (3)0.018 (3)−0.003 (2)0.000 (2)0.000 (2)
C60.018 (3)0.011 (2)0.022 (3)0.000 (2)0.003 (2)0.001 (2)
S70.0199 (8)0.0254 (7)0.0299 (8)−0.0009 (6)0.0056 (6)−0.0038 (6)
C80.031 (3)0.027 (3)0.017 (3)−0.008 (3)0.005 (2)−0.007 (2)
C90.022 (3)0.027 (3)0.023 (3)−0.008 (3)−0.003 (2)−0.001 (2)
C100.0124 (18)0.0140 (17)0.0192 (18)−0.0028 (15)0.0035 (14)−0.0001 (14)
C110.0154 (19)0.0203 (19)0.0215 (18)−0.0012 (16)0.0032 (15)−0.0036 (15)
S120.0168 (10)0.0152 (15)0.0226 (10)−0.0020 (12)−0.0010 (7)0.0007 (9)
C120.0168 (10)0.0152 (15)0.0226 (10)−0.0020 (12)−0.0010 (7)0.0007 (9)
C130.023 (3)0.038 (4)0.029 (3)−0.006 (3)0.001 (2)0.000 (3)
C140.018 (3)0.034 (3)0.038 (3)0.005 (3)0.006 (3)0.014 (3)
C150.0199 (16)0.019 (2)0.0227 (17)−0.0020 (17)−0.0010 (13)−0.0084 (16)
S150.0199 (16)0.019 (2)0.0227 (17)−0.0020 (17)−0.0010 (13)−0.0084 (16)
C160.011 (3)0.021 (3)0.021 (3)−0.003 (2)−0.001 (2)−0.001 (2)
C170.0134 (18)0.0159 (18)0.0178 (17)−0.0018 (15)0.0006 (14)−0.0025 (14)
C180.0126 (18)0.0162 (18)0.0193 (18)0.0005 (15)0.0016 (14)−0.0022 (15)
N190.014 (2)0.029 (3)0.030 (3)0.003 (2)0.0006 (19)−0.004 (2)
C200.0141 (18)0.0163 (18)0.0171 (17)−0.0001 (16)−0.0002 (14)−0.0016 (15)
C210.015 (3)0.024 (3)0.026 (3)−0.001 (2)0.004 (2)−0.002 (2)
C220.013 (3)0.024 (3)0.035 (3)0.009 (3)−0.001 (2)−0.004 (2)
C230.017 (3)0.021 (3)0.031 (3)0.008 (3)−0.003 (2)−0.001 (2)
C240.017 (3)0.027 (3)0.019 (3)0.000 (3)−0.003 (2)0.000 (2)
C250.007 (3)0.019 (3)0.025 (3)0.002 (2)−0.003 (2)−0.008 (2)
Geometric parameters (Å, °) top
S1—C21.721 (5)C12—H120.9300
S1—C51.722 (5)C13—C141.309 (7)
C2—C31.366 (6)C13—H130.9300
C2—C61.449 (6)C14—C151.446 (11)
C3—C41.431 (6)C14—S151.653 (5)
C3—C161.448 (6)C14—H140.9300
C4—C51.360 (6)C15—H150.9300
C4—H40.9300C16—C171.335 (6)
C5—C111.447 (6)C16—H160.9300
C6—C101.394 (6)C17—C181.422 (6)
C6—S71.720 (5)C17—C201.479 (6)
S7—C81.706 (5)C18—N191.148 (5)
C8—C91.342 (7)C20—C251.380 (6)
C8—H80.9300C20—C211.384 (6)
C9—C101.404 (6)C21—C221.378 (7)
C9—H90.9300C21—H210.9300
C10—H100.9300C22—C231.376 (7)
C11—C151.369 (10)C22—H220.9300
C11—C121.53 (4)C23—C241.370 (6)
C11—S151.670 (4)C23—H230.9300
C11—S121.688 (5)C24—C251.382 (7)
S12—C131.650 (6)C24—H240.9300
C12—C131.402 (5)C25—H250.9300
C2—S1—C592.1 (2)C14—C13—H13121.2
C3—C2—C6128.5 (4)C12—C13—H13129.5
C3—C2—S1111.7 (3)S12—C13—H13121.4
C6—C2—S1119.8 (3)C13—C14—C15106.1 (6)
C2—C3—C4111.7 (4)C13—C14—S15119.5 (4)
C2—C3—C16122.3 (4)C13—C14—H14126.9
C4—C3—C16125.9 (4)C15—C14—H14127.0
C5—C4—C3113.5 (4)S15—C14—H14113.6
C5—C4—H4123.3C11—C15—C14116.2 (7)
C3—C4—H4123.2C11—C15—H15121.9
C4—C5—C11127.5 (4)C14—C15—H15121.9
C4—C5—S1110.9 (3)C14—S15—C1192.0 (3)
C11—C5—S1121.3 (4)C17—C16—C3128.4 (5)
C10—C6—C2128.7 (4)C17—C16—H16115.8
C10—C6—S7110.2 (3)C3—C16—H16115.8
C2—C6—S7121.0 (3)C16—C17—C18120.9 (4)
C8—S7—C692.2 (2)C16—C17—C20124.3 (4)
C9—C8—S7111.6 (4)C18—C17—C20114.8 (4)
C9—C8—H8124.2N19—C18—C17178.7 (5)
S7—C8—H8124.2C25—C20—C21118.6 (5)
C8—C9—C10114.1 (5)C25—C20—C17120.3 (4)
C8—C9—H9123.0C21—C20—C17121.1 (4)
C10—C9—H9123.0C22—C21—C20120.6 (5)
C6—C10—C9111.8 (4)C22—C21—H21119.7
C6—C10—H10124.1C20—C21—H21119.7
C9—C10—H10124.1C23—C22—C21120.2 (5)
C15—C11—C5130.7 (5)C23—C22—H22119.9
C5—C11—C12132.0 (7)C21—C22—H22119.9
C5—C11—S15119.7 (4)C24—C23—C22119.7 (5)
C12—C11—S15108.1 (7)C24—C23—H23120.1
C15—C11—S12107.4 (5)C22—C23—H23120.2
C5—C11—S12121.8 (3)C23—C24—C25120.3 (5)
C13—S12—C1192.7 (3)C23—C24—H24119.9
C13—C12—C11111 (2)C25—C24—H24119.9
C13—C12—H12130.0C20—C25—C24120.6 (5)
C11—C12—H12119.0C20—C25—H25119.7
C14—C13—C12109.3 (17)C24—C25—H25119.7
C14—C13—S12117.4 (4)
C5—S1—C2—C30.3 (4)C5—C11—S12—C13175.6 (4)
C5—S1—C2—C6−179.7 (4)C5—C11—C12—C13174.9 (13)
C6—C2—C3—C4179.5 (4)S15—C11—C12—C130(3)
S1—C2—C3—C4−0.5 (5)C11—C12—C13—C140(3)
C6—C2—C3—C163.2 (8)C11—S12—C13—C140.2 (5)
S1—C2—C3—C16−176.8 (4)S12—C13—C14—C151.7 (8)
C2—C3—C4—C50.5 (6)C12—C13—C14—S150(2)
C16—C3—C4—C5176.6 (4)C5—C11—C15—C14−173.9 (6)
C3—C4—C5—C11−174.8 (4)S15—C11—C15—C14−168 (5)
C3—C4—C5—S1−0.3 (5)S12—C11—C15—C143.5 (11)
C2—S1—C5—C40.0 (4)C13—C14—C15—C11−3.4 (12)
C2—S1—C5—C11174.9 (4)C13—C14—S15—C11−0.1 (7)
C3—C2—C6—C1043.0 (8)C15—C14—S15—C11−7(3)
S1—C2—C6—C10−137.0 (4)C5—C11—S15—C14−175.7 (4)
C3—C2—C6—S7−138.9 (4)C12—C11—S15—C140(2)
S1—C2—C6—S741.1 (5)C2—C3—C16—C17−158.0 (5)
C10—C6—S7—C80.0 (4)C4—C3—C16—C1726.3 (8)
C2—C6—S7—C8−178.5 (4)C3—C16—C17—C183.7 (8)
C6—S7—C8—C9−0.8 (4)C3—C16—C17—C20−175.3 (4)
S7—C8—C9—C101.4 (6)C16—C17—C20—C2522.4 (7)
C2—C6—C10—C9179.1 (5)C18—C17—C20—C25−156.6 (4)
S7—C6—C10—C90.8 (5)C16—C17—C20—C21−157.5 (5)
C8—C9—C10—C6−1.5 (6)C18—C17—C20—C2123.4 (6)
C4—C5—C11—C15−148.9 (9)C25—C20—C21—C222.3 (7)
S1—C5—C11—C1537.0 (10)C17—C20—C21—C22−177.7 (4)
C4—C5—C11—C1235 (3)C20—C21—C22—C23−1.3 (7)
S1—C5—C11—C12−139 (2)C21—C22—C23—C240.0 (7)
C4—C5—C11—S15−150.2 (6)C22—C23—C24—C250.1 (7)
S1—C5—C11—S1535.7 (6)C21—C20—C25—C24−2.2 (7)
C4—C5—C11—S1234.0 (7)C17—C20—C25—C24177.9 (4)
S1—C5—C11—S12−140.1 (4)C23—C24—C25—C201.0 (7)
C15—C11—S12—C13−2.1 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C13—H13···N19i0.932.543.435 (7)161
Symmetry codes: (i) −x+1, −y, −z−1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C13—H13···N19i0.932.543.435 (7)161
Symmetry codes: (i) −x+1, −y, −z−1.
references
References top

Bruker (1996). XSCANS. Version 2.2. Bruker AXS Inc., Madison, Wisconsin, USA.

Clarke, T. M., Gordon, K. C., Wagner, P. & Officer, D. L. (2007). J. Phys. Chem. A, 111, 2385–2397.

Collis, G. A., Burrell, A. K., Scott, S. M. & Officer, D. L. (2003). J. Org. Chem. 68, 8974–8983.

Grant, D. K. & Officer, D. L. (2005). Synth. Met. 154, 93–95.

Roncali, J. (1999). Annu. Rep. Prog. Chem. Sect. C Phys. Chem. 95, 47–88.

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

Siemens (1989). Stereochemical Workstation Operation Manual. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Skotheim, T. A. & Reynolds, J. R. (2007). Handbook of Conducting Polymers, 3rd ed. New York: Taylor & Francis Group.

Sonar, V. N., Parkin, S. & Crooks, P. A. (2004). Acta Cryst. C60, o217–o218.

Sonar, V. N., Parkin, S. & Crooks, P. A. (2005). Acta Cryst. E61, o933–o935.

Wagner, P., Officer, D. L. & Kubicki, M. (2006). Acta Cryst. E62, o5745–o5747.

Wagner, P., Officer, D. L. & Kubicki, M. (2007). Acta Cryst. C63. In the press.. DN3048?