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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1877.
Published online 2010 June 30. doi:  10.1107/S1600536810013656
PMCID: PMC3006845

2,2′-[(1E,1′E)-2,2′-(2,5-Dibut­oxy-1,4-phenyl­ene)bis­(ethene-2,1-di­yl)]dipyridine

Abstract

The centrosymmetric title mol­ecule, C28H32N2O2, has a central benzene ring subsituted in the 1- and 4-positions by (ethene-2,1-di­yl)pyridine groups, and in the 2- and 5-positions by but­oxy groups. The whole mol­ecule is X-shaped and relatively flat, the dihedral angle between the pyridine and the central benzene ring being 11.29 (10)°. In the crystal, neighboring mol­ecules are linked by weak C—H(...)N inter­actions, forming a two-dimensional undulating network.

Related literature

For information on pyridine-based photo-refractive materials, see: Naumov et al. (2002 [triangle]); Liu et al. (2008 [triangle]).

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Object name is e-66-o1877-scheme1.jpg

Experimental

Crystal data

  • C28H32N2O2
  • M r = 428.56
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1877-efi1.jpg
  • a = 8.882 (5) Å
  • b = 13.892 (5) Å
  • c = 10.387 (5) Å
  • β = 107.392 (5)°
  • V = 1223.0 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.07 mm−1
  • T = 298 K
  • 0.50 × 0.30 × 0.20 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.964, T max = 0.986
  • 8512 measured reflections
  • 2162 independent reflections
  • 1385 reflections with I > 2σ(I)
  • R int = 0.040

Refinement

  • R[F 2 > 2σ(F 2)] = 0.049
  • wR(F 2) = 0.154
  • S = 1.03
  • 2162 reflections
  • 146 parameters
  • H-atom parameters constrained
  • Δρmax = 0.16 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg & Putz, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810013656/su2172sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013656/su2172Isup2.hkl

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant Nos. 50532030, 20771001 and 50703001) and the Team for Scientific Innovation Foundation of Anhui Province (grant No. 2006 K J007TD).

supplementary crystallographic information

Comment

Pyridine based materials have been investigated for their electrical and optical properties. The introduction of substituents in the 2- and 4-positions of pyridine represents a possible approach for designing pyridine-based photo-refractive materials (Naumov et al., 2002; Liu et al., 2008).

In the title molecule (Fig. 1), which is centrosymmetric, there are two pyridine rings and a central benzene ring. The dihedral angle between the pyridine and the central benzene ring is 11.29 (10) °.

In the crystal structure of the title compound there exist C5—H5···N1i interactions between neighboring molecules [see Fig. 2 and Table 1]. This leads to the formation of a two-dimensional network lieing parallel to the bc-plane.

Experimental

The title compound was prepared by firstly placing t-BuOK (8.98 g, 0.080 mol) in a dry motar and milling it to give very small particles. Then 2,5-Dibutoxy-1,4-bis(triphenylphosphonium)benzene dischloride (8.45 g, 0.010 mol) and picolinaldehyde (4.28 g, 0.040 mol) were added. The mixture was then milled vigorously for about 10 min. After the reaction was completed (monitored by TLC), the mixture was dispersed in 50 ml of H2O. The solution was extracted three times with 50 ml dichloromethane. The dichloromethane solution was dried for 12 h and concentrated. The concentrated solution was passed over a silica gel column and eluted with peroleum ether/ethyl acetate (8:1). By slow evaporation of the solvent yellow block-like crystals were obtained in 75% yield.

Refinement

The H-atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms: C—H = 0.93, 0.96 and 0.97 Å for CH, CH3 and CH2 H-atoms, respectively, with Uiso(H) = k × Ueq(parent C-atom), where k = 1.2 for CH and CH2 H-atoms and = 1.5 for CH3 H-atoms.

Figures

Fig. 1.
The molecular structure of the title molecule.
Fig. 2.
A view of the intermolecular C-H···N interactions (dashed lines) in the crystal structure of the title compound.

Crystal data

C28H32N2O2F(000) = 460
Mr = 428.56Dx = 1.164 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 1446 reflections
a = 8.882 (5) Åθ = 2.5–21.8°
b = 13.892 (5) ŵ = 0.07 mm1
c = 10.387 (5) ÅT = 298 K
β = 107.392 (5)°Block, yellow
V = 1223.0 (10) Å30.50 × 0.30 × 0.20 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer2162 independent reflections
Radiation source: fine-focus sealed tube1385 reflections with I > 2σ(I)
graphiteRint = 0.040
phi and ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −10→10
Tmin = 0.964, Tmax = 0.986k = −16→16
8512 measured reflectionsl = −11→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0821P)2 + 0.0525P] where P = (Fo2 + 2Fc2)/3
2162 reflections(Δ/σ)max < 0.001
146 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = −0.16 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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)

xyzUiso*/Ueq
O1−0.10160 (17)0.50961 (9)0.22161 (12)0.0589 (4)
C20.0431 (2)0.57863 (13)0.43825 (17)0.0477 (5)
H20.07250.63130.39600.057*
C1−0.0472 (2)0.50707 (13)0.36022 (17)0.0458 (5)
C50.2548 (2)0.72369 (13)0.61936 (18)0.0491 (5)
H50.23240.73100.52650.059*
C40.1898 (2)0.64922 (13)0.66286 (18)0.0487 (5)
H40.20830.64420.75560.058*
C60.3587 (2)0.79507 (14)0.70512 (19)0.0500 (5)
C30.0919 (2)0.57414 (13)0.57915 (17)0.0447 (5)
N10.3841 (2)0.78919 (14)0.83829 (17)0.0781 (6)
C70.4305 (3)0.86549 (15)0.6486 (2)0.0617 (6)
H70.41060.86890.55560.074*
C11−0.0751 (3)0.59382 (15)0.15295 (19)0.0620 (6)
H11A0.03590.59960.16010.074*
H11B−0.10690.65070.19220.074*
C12−0.1717 (3)0.58404 (16)0.00746 (18)0.0639 (6)
H12A−0.15030.5217−0.02530.077*
H12B−0.28260.58570.00200.077*
C80.5312 (3)0.93013 (17)0.7318 (3)0.0770 (7)
H80.57970.97800.69570.092*
C100.4832 (3)0.8533 (2)0.9145 (2)0.0988 (10)
H100.50180.84981.00740.119*
C90.5588 (3)0.9232 (2)0.8671 (3)0.0907 (9)
H90.62770.96520.92580.109*
C13−0.1405 (4)0.6606 (2)−0.0831 (2)0.0963 (9)
H13A−0.03020.6582−0.07950.116*
H13B−0.16030.7231−0.04990.116*
C14−0.2407 (4)0.6502 (2)−0.2276 (2)0.0996 (10)
H14A−0.22730.5868−0.25940.149*
H14B−0.20920.6972−0.28220.149*
H14C−0.34960.6599−0.23350.149*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0777 (10)0.0571 (9)0.0353 (8)−0.0123 (7)0.0069 (7)−0.0006 (6)
C20.0541 (12)0.0462 (10)0.0408 (11)−0.0014 (9)0.0111 (9)−0.0001 (8)
C10.0492 (11)0.0514 (11)0.0330 (10)0.0032 (9)0.0066 (9)−0.0017 (8)
C50.0514 (12)0.0543 (12)0.0386 (11)0.0007 (9)0.0090 (9)−0.0031 (9)
C40.0550 (12)0.0529 (11)0.0346 (11)−0.0021 (9)0.0081 (9)−0.0050 (8)
C60.0510 (12)0.0529 (12)0.0467 (12)−0.0029 (9)0.0155 (10)−0.0073 (9)
C30.0466 (11)0.0463 (11)0.0387 (10)0.0006 (8)0.0090 (9)−0.0034 (8)
N10.0928 (15)0.0965 (15)0.0456 (11)−0.0454 (12)0.0215 (10)−0.0188 (10)
C70.0672 (14)0.0618 (13)0.0568 (13)−0.0111 (11)0.0194 (11)−0.0026 (10)
C110.0807 (16)0.0550 (13)0.0478 (12)−0.0075 (11)0.0154 (11)0.0028 (10)
C120.0770 (16)0.0679 (14)0.0421 (12)−0.0073 (11)0.0107 (11)0.0048 (10)
C80.0811 (17)0.0685 (15)0.0898 (19)−0.0262 (13)0.0385 (14)−0.0114 (13)
C100.115 (2)0.129 (2)0.0536 (15)−0.067 (2)0.0270 (15)−0.0310 (15)
C90.0903 (19)0.105 (2)0.0823 (19)−0.0484 (16)0.0338 (15)−0.0386 (16)
C130.131 (2)0.0873 (18)0.0572 (16)−0.0271 (17)0.0078 (16)0.0158 (13)
C140.125 (3)0.108 (2)0.0532 (15)−0.0132 (18)0.0064 (15)0.0242 (14)

Geometric parameters (Å, °)

O1—C11.375 (2)C11—C121.504 (3)
O1—C111.426 (2)C11—H11A0.9700
C2—C11.379 (3)C11—H11B0.9700
C2—C31.398 (2)C12—C131.499 (3)
C2—H20.9300C12—H12A0.9700
C1—C3i1.406 (3)C12—H12B0.9700
C5—C41.328 (3)C8—C91.356 (3)
C5—C61.462 (3)C8—H80.9300
C5—H50.9300C10—C91.353 (3)
C4—C31.466 (3)C10—H100.9300
C4—H40.9300C9—H90.9300
C6—N11.336 (2)C13—C141.506 (3)
C6—C71.390 (3)C13—H13A0.9700
C3—C1i1.406 (3)C13—H13B0.9700
N1—C101.334 (3)C14—H14A0.9600
C7—C81.375 (3)C14—H14B0.9600
C7—H70.9300C14—H14C0.9600
C1—O1—C11119.07 (14)H11A—C11—H11B108.5
C1—C2—C3121.80 (18)C13—C12—C11114.19 (19)
C1—C2—H2119.1C13—C12—H12A108.7
C3—C2—H2119.1C11—C12—H12A108.7
O1—C1—C2123.88 (17)C13—C12—H12B108.7
O1—C1—C3i115.58 (15)C11—C12—H12B108.7
C2—C1—C3i120.53 (17)H12A—C12—H12B107.6
C4—C5—C6125.48 (18)C9—C8—C7119.1 (2)
C4—C5—H5117.3C9—C8—H8120.4
C6—C5—H5117.3C7—C8—H8120.4
C5—C4—C3126.43 (18)N1—C10—C9125.0 (2)
C5—C4—H4116.8N1—C10—H10117.5
C3—C4—H4116.8C9—C10—H10117.5
N1—C6—C7121.57 (18)C10—C9—C8118.2 (2)
N1—C6—C5118.03 (18)C10—C9—H9120.9
C7—C6—C5120.38 (18)C8—C9—H9120.9
C2—C3—C1i117.66 (16)C12—C13—C14113.1 (2)
C2—C3—C4122.17 (17)C12—C13—H13A109.0
C1i—C3—C4120.15 (16)C14—C13—H13A109.0
C10—N1—C6116.8 (2)C12—C13—H13B109.0
C8—C7—C6119.3 (2)C14—C13—H13B109.0
C8—C7—H7120.4H13A—C13—H13B107.8
C6—C7—H7120.4C13—C14—H14A109.5
O1—C11—C12107.37 (16)C13—C14—H14B109.5
O1—C11—H11A110.2H14A—C14—H14B109.5
C12—C11—H11A110.2C13—C14—H14C109.5
O1—C11—H11B110.2H14A—C14—H14C109.5
C12—C11—H11B110.2H14B—C14—H14C109.5

Symmetry codes: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C5—H5···N1ii0.932.703.446 (3)138

Symmetry codes: (ii) x, −y+3/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2172).

References

  • Brandenburg, K. & Putz, H. (2008). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Liu, H. J., Tao, X. T., Yang, J. X., Yan, Y. X., Ren, Y., Zhao, H. P., Xin, Q., Yu, W. T. & Jiang, M. H. (2008). Cryst. Growth Des.8, 259–264.
  • Naumov, P., Sekine, A., Uekusa, H. & Ohashi, Y. (2002). J. Am. Chem. Soc.124, 8540–8541. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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