9-Allyl-9H-carbazole-3,6-dicarbaldehyde

Bin Bin Hu; Xiang Chao Zeng; Lei Bian; Ru He

doi:10.1107/S160053681203190X

. 2012 Jul 21;68(Pt 8):o2517. doi: 10.1107/S160053681203190X

9-Allyl-9H-carbazole-3,6-dicarbaldehyde

Bin Bin Hu ^a, Xiang Chao Zeng ^a,^*, Lei Bian ^a, Ru He ^a

PMCID: PMC3414967 PMID: 22904954

Abstract

In the title molecule, C₁₇H₁₃NO₂, the allyl group is almost perpendicular to the carbazole mean plane, with a dihedral angle of 89.0 (2)°. In the crystal, nonclassical C—H⋯O hydrogen bonds link the molecules into corrugated sheets parallel to the bc plane. Weak intermolecular π–π interactions are observed between the benzene rings [centroid–centroid distance = 3.874 (4) Å] from neighbouring sheets.

Related literature

For applications of carbazole derivatives, see: Hong et al. (2012 ▶); Samanta et al. (2001 ▶); Koyuncua et al. (2011 ▶); Zhang et al. (2010 ▶). For related structures, see: Wang et al. (2008 ▶); Zhao et al. (2012 ▶).

Experimental

Crystal data

C₁₇H₁₃NO₂
M _r = 263.28
Monoclinic,
a = 8.4062 (8) Å
b = 10.3279 (10) Å
c = 15.2432 (19) Å
β = 94.958 (9)°
V = 1318.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.44 × 0.28 × 0.26 mm

Data collection

Oxford Gemini S Ultra area-detector diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.963, T _max = 0.978
5464 measured reflections
2835 independent reflections
1909 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.118
S = 1.02
2835 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681203190X/cv5316sup1.cif

e-68-o2517-sup1.cif^{(18KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681203190X/cv5316Isup2.hkl

e-68-o2517-Isup2.hkl^{(139.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681203190X/cv5316Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.58	3.489 (3)	166
C5—H5⋯O2ⁱⁱ	0.93	2.54	3.332 (2)	143

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work has been supported by the Natural Science Foundation of Guangdong Province, China (grant No. 06300581).

supplementary crystallographic information

Comment

The carbazole ring has a highly conjugated π system with desirable optical and charge-transport properties, and these characteristics make carozole derivatives the excellent candidates to yield materials for applications in different areas of science, such as dye-sensitized solar cell (Hong et al., 2012), electroluminescent (Samanta et al., 2001), electrochromic displays (Koyuncua et al., 2011) and antibacterial and antitumor agents (Zhang et al., 2010). These are the reasons why they have attracted our interest. Here we report the crystal structure of the title compound which consists of a carbazole skeleton with a allyl group and two formacyls (Fig. 1).

In the title molecule, the bond lengths and angles are unexceptional, and generally agree with those observed in the related compounds (Wang et al., 2008; Zhao et al., 2012). The non-H atoms of the carbazole ring and the two formacyls are approximately coplanar with r.m.s. deviation from the best fit plane of 0.006 (3) °, the allyl group is almost perpendicular to the carbazole mean plane with a dihedral angle of 89.0 (2)°. In the crystal, C2—H···O1 and C5—H···O2 non-classical H-bonds (Table 1) link the molecules into corrugated sheets parallel to bc plane (Fig. 2). Weak intermolecular π–π interactions between the benzene rings [centroid-centroid distance = 3.874 (4) Å] from the neighbouring sheets stabilize further the crystal packing.

Experimental

Phosphorus oxychloride (2.0 ml, 20 mmol) was added dropwise to the mixture of dry dimethylformamide (DMF, 3.0 ml, 40 mmol) and 9-allylcarbazole (2.07 g, 10 mmol) in chlorobenzene (20 ml) at 273 K under stirring. This solution was warmed up slowly to the room temperature in 0.5 h and stirred for another 0.5 h. After standing for 18 h at 343 K, more 3 ml DMF and 2 ml phosphorus oxychloride were added and stirred for 18 h continuously at the same temperature. After cooling, the resulting mixture was neutralized with saturated sodium bicarbonate solution until pH reached a value of 6 - 7, then the chlorobenzene was removed by water steam distillation, and the product was extracted with chloroform. After washing three times with water, the organic layer was dried over magnesium sulfate and evaporated in vacuo. The residue was separated by silica-gel column chromatography using petroleum ether-ethyl acetate (10:1) as eluting solvent and the title compound (I) was obtained (55.2% yield). Light brown crystals suitable for X-ray analysis (m.p. 429 K) grew over a period of one week when the ethyl acetate solution of I was exposed to the air at room temperature.