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

Zhang, R.-L.; Liu, Z.-D.; Wu, J.-Y.

doi:10.1107/S1600536810013656

organic compounds

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Volume 66| Part 7| July 2010| Page o1877

doi:10.1107/S1600536810013656

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

Rui-Long Zhang,^a Zhao-Di Liu ^a and Jie-Ying Wu ^a ^*

^aDepartment of Chemistry, Anhui University, Hefei 230039, People's Republic of China, and Key Laboratory of Functional Inorganic Materials Chemistry, Hefei 230039, People's Republic of China
^*Correspondence e-mail: jywu1957@163.com

(Received 30 March 2010; accepted 13 April 2010; online 30 June 2010)

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 ); Liu et al. (2008 ).

Experimental

Crystal data

C₂₈H₃₂N₂O₂
M_r = 428.56
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.049
wR(F²) = 0.154
S = 1.03
2162 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯N1ⁱ	0.93	2.70	3.446 (3)	138
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

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

Crystal data top

C₂₈H₃₂N₂O₂	F(000) = 460
M_r = 428.56	D_x = 1.164 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 1446 reflections
a = 8.882 (5) Å	θ = 2.5–21.8°
b = 13.892 (5) Å	µ = 0.07 mm⁻¹
c = 10.387 (5) Å	T = 298 K
β = 107.392 (5)°	Block, yellow
V = 1223.0 (10) Å³	0.50 × 0.30 × 0.20 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2162 independent reflections
Radiation source: fine-focus sealed tube	1385 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
phi and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.964, T_max = 0.986	k = −16→16
8512 measured reflections	l = −11→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0821P)² + 0.0525P] where P = (F_o² + 2F_c²)/3
2162 reflections	(Δ/σ)_max < 0.001
146 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₂₈H₃₂N₂O₂	V = 1223.0 (10) Å³
M_r = 428.56	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.882 (5) Å	µ = 0.07 mm⁻¹
b = 13.892 (5) Å	T = 298 K
c = 10.387 (5) Å	0.50 × 0.30 × 0.20 mm
β = 107.392 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2162 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1385 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.986	R_int = 0.040
8512 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.154	H-atom parameters constrained
S = 1.03	Δρ_max = 0.16 e Å⁻³
2162 reflections	Δρ_min = −0.16 e Å⁻³
146 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	−0.10160 (17)	0.50961 (9)	0.22161 (12)	0.0589 (4)
C2	0.0431 (2)	0.57863 (13)	0.43825 (17)	0.0477 (5)
H2	0.0725	0.6313	0.3960	0.057*
C1	−0.0472 (2)	0.50707 (13)	0.36022 (17)	0.0458 (5)
C5	0.2548 (2)	0.72369 (13)	0.61936 (18)	0.0491 (5)
H5	0.2324	0.7310	0.5265	0.059*
C4	0.1898 (2)	0.64922 (13)	0.66286 (18)	0.0487 (5)
H4	0.2083	0.6442	0.7556	0.058*
C6	0.3587 (2)	0.79507 (14)	0.70512 (19)	0.0500 (5)
C3	0.0919 (2)	0.57414 (13)	0.57915 (17)	0.0447 (5)
N1	0.3841 (2)	0.78919 (14)	0.83829 (17)	0.0781 (6)
C7	0.4305 (3)	0.86549 (15)	0.6486 (2)	0.0617 (6)
H7	0.4106	0.8689	0.5556	0.074*
C11	−0.0751 (3)	0.59382 (15)	0.15295 (19)	0.0620 (6)
H11A	0.0359	0.5996	0.1601	0.074*
H11B	−0.1069	0.6507	0.1922	0.074*
C12	−0.1717 (3)	0.58404 (16)	0.00746 (18)	0.0639 (6)
H12A	−0.1503	0.5217	−0.0253	0.077*
H12B	−0.2826	0.5857	0.0020	0.077*
C8	0.5312 (3)	0.93013 (17)	0.7318 (3)	0.0770 (7)
H8	0.5797	0.9780	0.6957	0.092*
C10	0.4832 (3)	0.8533 (2)	0.9145 (2)	0.0988 (10)
H10	0.5018	0.8498	1.0074	0.119*
C9	0.5588 (3)	0.9232 (2)	0.8671 (3)	0.0907 (9)
H9	0.6277	0.9652	0.9258	0.109*
C13	−0.1405 (4)	0.6606 (2)	−0.0831 (2)	0.0963 (9)
H13A	−0.0302	0.6582	−0.0795	0.116*
H13B	−0.1603	0.7231	−0.0499	0.116*
C14	−0.2407 (4)	0.6502 (2)	−0.2276 (2)	0.0996 (10)
H14A	−0.2273	0.5868	−0.2594	0.149*
H14B	−0.2092	0.6972	−0.2822	0.149*
H14C	−0.3496	0.6599	−0.2335	0.149*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0777 (10)	0.0571 (9)	0.0353 (8)	−0.0123 (7)	0.0069 (7)	−0.0006 (6)
C2	0.0541 (12)	0.0462 (10)	0.0408 (11)	−0.0014 (9)	0.0111 (9)	−0.0001 (8)
C1	0.0492 (11)	0.0514 (11)	0.0330 (10)	0.0032 (9)	0.0066 (9)	−0.0017 (8)
C5	0.0514 (12)	0.0543 (12)	0.0386 (11)	0.0007 (9)	0.0090 (9)	−0.0031 (9)
C4	0.0550 (12)	0.0529 (11)	0.0346 (11)	−0.0021 (9)	0.0081 (9)	−0.0050 (8)
C6	0.0510 (12)	0.0529 (12)	0.0467 (12)	−0.0029 (9)	0.0155 (10)	−0.0073 (9)
C3	0.0466 (11)	0.0463 (11)	0.0387 (10)	0.0006 (8)	0.0090 (9)	−0.0034 (8)
N1	0.0928 (15)	0.0965 (15)	0.0456 (11)	−0.0454 (12)	0.0215 (10)	−0.0188 (10)
C7	0.0672 (14)	0.0618 (13)	0.0568 (13)	−0.0111 (11)	0.0194 (11)	−0.0026 (10)
C11	0.0807 (16)	0.0550 (13)	0.0478 (12)	−0.0075 (11)	0.0154 (11)	0.0028 (10)
C12	0.0770 (16)	0.0679 (14)	0.0421 (12)	−0.0073 (11)	0.0107 (11)	0.0048 (10)
C8	0.0811 (17)	0.0685 (15)	0.0898 (19)	−0.0262 (13)	0.0385 (14)	−0.0114 (13)
C10	0.115 (2)	0.129 (2)	0.0536 (15)	−0.067 (2)	0.0270 (15)	−0.0310 (15)
C9	0.0903 (19)	0.105 (2)	0.0823 (19)	−0.0484 (16)	0.0338 (15)	−0.0386 (16)
C13	0.131 (2)	0.0873 (18)	0.0572 (16)	−0.0271 (17)	0.0078 (16)	0.0158 (13)
C14	0.125 (3)	0.108 (2)	0.0532 (15)	−0.0132 (18)	0.0064 (15)	0.0242 (14)

Geometric parameters (Å, º) top

O1—C1	1.375 (2)	C11—C12	1.504 (3)
O1—C11	1.426 (2)	C11—H11A	0.9700
C2—C1	1.379 (3)	C11—H11B	0.9700
C2—C3	1.398 (2)	C12—C13	1.499 (3)
C2—H2	0.9300	C12—H12A	0.9700
C1—C3ⁱ	1.406 (3)	C12—H12B	0.9700
C5—C4	1.328 (3)	C8—C9	1.356 (3)
C5—C6	1.462 (3)	C8—H8	0.9300
C5—H5	0.9300	C10—C9	1.353 (3)
C4—C3	1.466 (3)	C10—H10	0.9300
C4—H4	0.9300	C9—H9	0.9300
C6—N1	1.336 (2)	C13—C14	1.506 (3)
C6—C7	1.390 (3)	C13—H13A	0.9700
C3—C1ⁱ	1.406 (3)	C13—H13B	0.9700
N1—C10	1.334 (3)	C14—H14A	0.9600
C7—C8	1.375 (3)	C14—H14B	0.9600
C7—H7	0.9300	C14—H14C	0.9600

C1—O1—C11	119.07 (14)	H11A—C11—H11B	108.5
C1—C2—C3	121.80 (18)	C13—C12—C11	114.19 (19)
C1—C2—H2	119.1	C13—C12—H12A	108.7
C3—C2—H2	119.1	C11—C12—H12A	108.7
O1—C1—C2	123.88 (17)	C13—C12—H12B	108.7
O1—C1—C3ⁱ	115.58 (15)	C11—C12—H12B	108.7
C2—C1—C3ⁱ	120.53 (17)	H12A—C12—H12B	107.6
C4—C5—C6	125.48 (18)	C9—C8—C7	119.1 (2)
C4—C5—H5	117.3	C9—C8—H8	120.4
C6—C5—H5	117.3	C7—C8—H8	120.4
C5—C4—C3	126.43 (18)	N1—C10—C9	125.0 (2)
C5—C4—H4	116.8	N1—C10—H10	117.5
C3—C4—H4	116.8	C9—C10—H10	117.5
N1—C6—C7	121.57 (18)	C10—C9—C8	118.2 (2)
N1—C6—C5	118.03 (18)	C10—C9—H9	120.9
C7—C6—C5	120.38 (18)	C8—C9—H9	120.9
C2—C3—C1ⁱ	117.66 (16)	C12—C13—C14	113.1 (2)
C2—C3—C4	122.17 (17)	C12—C13—H13A	109.0
C1ⁱ—C3—C4	120.15 (16)	C14—C13—H13A	109.0
C10—N1—C6	116.8 (2)	C12—C13—H13B	109.0
C8—C7—C6	119.3 (2)	C14—C13—H13B	109.0
C8—C7—H7	120.4	H13A—C13—H13B	107.8
C6—C7—H7	120.4	C13—C14—H14A	109.5
O1—C11—C12	107.37 (16)	C13—C14—H14B	109.5
O1—C11—H11A	110.2	H14A—C14—H14B	109.5
C12—C11—H11A	110.2	C13—C14—H14C	109.5
O1—C11—H11B	110.2	H14A—C14—H14C	109.5
C12—C11—H11B	110.2	H14B—C14—H14C	109.5

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N1ⁱⁱ	0.93	2.70	3.446 (3)	138

Symmetry code: (ii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₈H₃₂N₂O₂
M_r	428.56
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.882 (5), 13.892 (5), 10.387 (5)
β (°)	107.392 (5)
V (Å³)	1223.0 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.50 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.964, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	8512, 2162, 1385
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.154, 1.03
No. of reflections	2162
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.16

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N1ⁱ	0.93	2.70	3.446 (3)	138

Symmetry code: (i) x, −y+3/2, z−1/2.

Acknowledgements

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).

References

Brandenburg, K. & Putz, H. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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. Web of Science CSD CrossRef CAS Google Scholar
Naumov, P., Sekine, A., Uekusa, H. & Ohashi, Y. (2002). J. Am. Chem. Soc. 124, 8540–8541. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1877

doi:10.1107/S1600536810013656

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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