PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o1885.
Published online 2010 July 3. doi:  10.1107/S1600536810025183
PMCID: PMC3007555

9-Ethyl-9H-carbazole-3-carbaldehyde

Abstract

The title mol­ecule, C15H13NO, approximates a planar conformation except for the alkyl chain (ethyl group) bonded to the N atom with a maximum deviation from the least-squares plane through the 15 planar atoms of 0.120 (2) Å for the O atom. The distance of the formyl O atom from the plane of the carbazole ring is 0.227 (2) Å. The N—C bond lengths in the central ring are significantly different, reflecting the electron-withdrawing properties of the aldehyde group. As a consequence, charge transfer may occur from the carbazole N atom to the substituted benzene ring.

Related literature

For the properties of carbazole derivatives, see: van Dijken et al. (2004 [triangle]); Li et al. (2005 [triangle]). For the X-ray structure of 9-ethyl-3,6-diformyl-9H-carbazole, see: Wang et al. (2008 [triangle]) and of 9-ethyl-9H-carbazole, see: Kimura et al. (1985 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o1885-scheme1.jpg

Experimental

Crystal data

  • C15H13NO
  • M r = 223.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1885-efi1.jpg
  • a = 10.6523 (10) Å
  • b = 8.2312 (6) Å
  • c = 13.8005 (12) Å
  • β = 104.387 (1)°
  • V = 1172.10 (17) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 298 K
  • 0.50 × 0.44 × 0.43 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.961, T max = 0.967
  • 5763 measured reflections
  • 2065 independent reflections
  • 1313 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.116
  • S = 1.05
  • 2065 reflections
  • 155 parameters
  • H-atom parameters constrained
  • Δρmax = 0.13 e Å−3
  • Δρmin = −0.11 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [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: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810025183/bh2297sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025183/bh2297Isup2.hkl

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

Acknowledgments

This work was supported by the PhD Programs Foundation of the Ministry of Education of China (No. 20090204120033).

supplementary crystallographic information

Comment

Carbazole is a conjugated unit which has interesting optical and electronic properties. A number of carbazole derivatives have been designed and synthesized to be used as luminescent materials and hole-transporting materials (van Dijken et al., 2004; Li et al., 2005). In the course of exploring new luminescent compounds, we obtained an intermediate compound, 9-ethyl-3-formyl-9H-carbazole (I). Here we report the structure and synthesis of (I).

The molecule (Fig. 1) lies approximately in a plane besides the alkyl chain (ethyl group). There is a minor displacement between the oxygen atom O1 and the plane of the carbazole ring. And the distance from the oxygen atom O1 to the carbazole plane (the least-squares plane defined by all the 13 atoms of the carbazole framework) is 0.227 (2) Å. The remarkable difference of N—C bond lengths is observed in this structure: N1—C1 = 1.372 (3), N1—C12 = 1.391 (3) Å, which is obviously different from that of 9-ethyl-3,6-diformyl-9H-carbazole (Wang et al., 2008) and that of 9-ethyl-9H-carbazole (Kimura et al., 1985). The different N—C bond lengths maybe root from the structural asymmetry. The pull-electron property of aldehyde group induces a charge-transfer from nitrogen atom N1 to the benzene ring which connects with the aldehyde group.

The molecules are packed in P21/n space group, which is the same as for 9-ethyl-3,6-diformyl-9H-carbazole, but different from that of 9-ethyl-9H-carbazole (Pbca). There are no classic hydrogen bonds in this structure. However, the weak intermolecular interaction C11—H11···O1 (symmetry code for O1: x-1, y, z), is helpful to the stabilization of the crystal structure (Fig. 2). This intermolecular hydrogen bond is characterized by the H11···O1 separation of 2.54 Å.

Experimental

9-Ethyl-9H-carbazole (0.30 g, 1.54 mmol) was dissolved in N,N-dimethylformamide (DMF, 10 ml). After cooling the mixture to 273 K, a DMF solution of POCl3 (0.24 g, 1.60 mmol) was slowly added. After stirring for 10 h., the mixture was poured into ice water and further stirred for 0.5 h. The solution was extracted with chloroform and dried over Na2SO4. After removing the solvent, the crude product was purified by recrystallization from ethanol, affording the title compound, (I) (0.29 g, 85%). Then, compound (I) was dissolved in a mixture of solvents, chloroform and hexane, and colorless block crystals were formed on slow evaporation at room temperature over one week.

Refinement

All H atoms were placed in geometrically calculated positions and refined using a riding model with C—H = 0.93 Å (for aromatic CH), C—H = 0.97 %A (for CH2 groups), and 0.96 %A (for CH3 groups). Their isotropic displacement parameters were set to 1.2 times (1.5 times for CH3 groups) the equivalent displacement parameter of their parent atoms.

Figures

Fig. 1.
The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A view of the molecular packing of (I) along axis b.

Crystal data

C15H13NOF(000) = 472
Mr = 223.26Dx = 1.265 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1960 reflections
a = 10.6523 (10) Åθ = 2.8–25.2°
b = 8.2312 (6) ŵ = 0.08 mm1
c = 13.8005 (12) ÅT = 298 K
β = 104.387 (1)°Block, colorless
V = 1172.10 (17) Å30.50 × 0.44 × 0.43 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer2065 independent reflections
Radiation source: fine-focus sealed tube1313 reflections with I > 2σ(I)
graphiteRint = 0.029
[var phi] and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −12→12
Tmin = 0.961, Tmax = 0.967k = −9→5
5763 measured reflectionsl = −16→16

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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0369P)2 + 0.3721P] where P = (Fo2 + 2Fc2)/3
2065 reflections(Δ/σ)max < 0.001
155 parametersΔρmax = 0.13 e Å3
0 restraintsΔρmin = −0.11 e Å3
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
N10.23808 (16)0.0604 (2)0.36043 (12)0.0579 (5)
O10.83067 (17)0.1354 (3)0.36513 (14)0.0966 (6)
C10.3591 (2)0.0376 (3)0.34470 (15)0.0518 (5)
C20.3972 (2)−0.0683 (3)0.27949 (16)0.0631 (6)
H20.3382−0.13830.23900.076*
C30.5250 (2)−0.0665 (3)0.27648 (16)0.0626 (6)
H30.5528−0.13820.23400.075*
C40.6142 (2)0.0397 (3)0.33530 (15)0.0545 (6)
C50.5753 (2)0.1450 (3)0.40056 (14)0.0529 (5)
H50.63470.21570.44010.063*
C60.44792 (19)0.1444 (2)0.40663 (13)0.0466 (5)
C70.37450 (19)0.2342 (2)0.46404 (14)0.0489 (5)
C80.4063 (2)0.3526 (3)0.53694 (16)0.0639 (6)
H80.49140.38860.55920.077*
C90.3104 (3)0.4162 (3)0.57591 (18)0.0766 (7)
H90.33040.49730.62420.092*
C100.1842 (3)0.3611 (3)0.54428 (19)0.0773 (7)
H100.12110.40630.57200.093*
C110.1490 (2)0.2417 (3)0.47318 (17)0.0666 (7)
H110.06400.20490.45240.080*
C120.2467 (2)0.1786 (3)0.43386 (15)0.0531 (5)
C130.7479 (2)0.0386 (3)0.32700 (18)0.0709 (7)
H130.7716−0.04390.28900.085*
C140.1223 (2)−0.0304 (3)0.31232 (18)0.0747 (7)
H14A0.1251−0.05610.24430.090*
H14B0.04670.03680.30920.090*
C150.1098 (3)−0.1842 (4)0.3666 (2)0.1012 (10)
H15A0.1832−0.25270.36790.152*
H15B0.0318−0.23950.33290.152*
H15C0.1065−0.15930.43390.152*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0484 (11)0.0677 (12)0.0556 (11)−0.0109 (9)0.0089 (8)−0.0058 (10)
O10.0640 (12)0.1300 (18)0.1015 (14)−0.0201 (12)0.0310 (10)0.0030 (13)
C10.0529 (13)0.0550 (13)0.0474 (12)−0.0049 (10)0.0122 (10)0.0044 (10)
C20.0631 (15)0.0672 (16)0.0590 (14)−0.0122 (12)0.0152 (11)−0.0083 (12)
C30.0731 (17)0.0609 (15)0.0577 (14)0.0011 (12)0.0239 (12)−0.0005 (12)
C40.0584 (14)0.0573 (14)0.0494 (12)−0.0012 (11)0.0169 (10)0.0115 (11)
C50.0529 (13)0.0560 (13)0.0480 (12)−0.0121 (10)0.0093 (10)0.0098 (11)
C60.0495 (12)0.0483 (12)0.0411 (11)−0.0056 (10)0.0093 (9)0.0083 (10)
C70.0567 (13)0.0473 (12)0.0427 (11)−0.0095 (10)0.0123 (9)0.0086 (10)
C80.0803 (17)0.0608 (15)0.0553 (13)−0.0202 (13)0.0257 (12)−0.0002 (12)
C90.109 (2)0.0605 (16)0.0702 (16)−0.0180 (15)0.0410 (15)−0.0074 (13)
C100.095 (2)0.0729 (17)0.0764 (17)0.0029 (16)0.0449 (15)0.0022 (15)
C110.0623 (15)0.0761 (17)0.0652 (14)−0.0018 (13)0.0228 (12)0.0092 (14)
C120.0581 (14)0.0559 (13)0.0454 (11)−0.0020 (11)0.0129 (10)0.0079 (11)
C130.0654 (17)0.0861 (19)0.0677 (16)0.0026 (14)0.0289 (13)0.0157 (14)
C140.0548 (15)0.097 (2)0.0704 (15)−0.0197 (13)0.0114 (12)−0.0166 (15)
C150.108 (2)0.108 (2)0.092 (2)−0.0571 (19)0.0328 (17)−0.0225 (19)

Geometric parameters (Å, °)

N1—C11.372 (3)C7—C121.398 (3)
N1—C121.391 (3)C8—C91.371 (3)
N1—C141.453 (3)C8—H80.9300
O1—C131.208 (3)C9—C101.382 (3)
C1—C21.384 (3)C9—H90.9300
C1—C61.413 (3)C10—C111.374 (3)
C2—C31.372 (3)C10—H100.9300
C2—H20.9300C11—C121.388 (3)
C3—C41.394 (3)C11—H110.9300
C3—H30.9300C13—H130.9300
C4—C51.385 (3)C14—C151.494 (4)
C4—C131.457 (3)C14—H14A0.9700
C5—C61.380 (3)C14—H14B0.9700
C5—H50.9300C15—H15A0.9600
C6—C71.447 (3)C15—H15B0.9600
C7—C81.381 (3)C15—H15C0.9600
C1—N1—C12108.45 (16)C8—C9—C10120.8 (2)
C1—N1—C14125.50 (19)C8—C9—H9119.6
C12—N1—C14125.96 (19)C10—C9—H9119.6
N1—C1—C2128.9 (2)C11—C10—C9122.1 (2)
N1—C1—C6109.47 (18)C11—C10—H10118.9
C2—C1—C6121.60 (19)C9—C10—H10118.9
C3—C2—C1117.8 (2)C10—C11—C12116.7 (2)
C3—C2—H2121.1C10—C11—H11121.7
C1—C2—H2121.1C12—C11—H11121.7
C2—C3—C4121.8 (2)C11—C12—N1128.8 (2)
C2—C3—H3119.1C11—C12—C7122.0 (2)
C4—C3—H3119.1N1—C12—C7109.22 (18)
C5—C4—C3120.0 (2)O1—C13—C4125.7 (3)
C5—C4—C13120.7 (2)O1—C13—H13117.1
C3—C4—C13119.2 (2)C4—C13—H13117.1
C6—C5—C4119.61 (19)N1—C14—C15112.2 (2)
C6—C5—H5120.2N1—C14—H14A109.2
C4—C5—H5120.2C15—C14—H14A109.2
C5—C6—C1119.12 (19)N1—C14—H14B109.2
C5—C6—C7134.79 (19)C15—C14—H14B109.2
C1—C6—C7106.09 (17)H14A—C14—H14B107.9
C8—C7—C12119.5 (2)C14—C15—H15A109.5
C8—C7—C6133.74 (19)C14—C15—H15B109.5
C12—C7—C6106.76 (18)H15A—C15—H15B109.5
C9—C8—C7118.9 (2)C14—C15—H15C109.5
C9—C8—H8120.6H15A—C15—H15C109.5
C7—C8—H8120.6H15B—C15—H15C109.5
C12—N1—C1—C2179.4 (2)C1—C6—C7—C12−0.3 (2)
C14—N1—C1—C22.6 (3)C12—C7—C8—C9−1.9 (3)
C12—N1—C1—C6−1.4 (2)C6—C7—C8—C9178.8 (2)
C14—N1—C1—C6−178.23 (19)C7—C8—C9—C101.1 (3)
N1—C1—C2—C3179.0 (2)C8—C9—C10—C110.0 (4)
C6—C1—C2—C3−0.1 (3)C9—C10—C11—C12−0.2 (3)
C1—C2—C3—C4−1.2 (3)C10—C11—C12—N1−178.6 (2)
C2—C3—C4—C51.4 (3)C10—C11—C12—C7−0.6 (3)
C2—C3—C4—C13−178.5 (2)C1—N1—C12—C11179.4 (2)
C3—C4—C5—C6−0.2 (3)C14—N1—C12—C11−3.8 (3)
C13—C4—C5—C6179.62 (18)C1—N1—C12—C71.2 (2)
C4—C5—C6—C1−1.0 (3)C14—N1—C12—C7178.0 (2)
C4—C5—C6—C7−179.8 (2)C8—C7—C12—C111.7 (3)
N1—C1—C6—C5−178.10 (17)C6—C7—C12—C11−178.88 (19)
C2—C1—C6—C51.2 (3)C8—C7—C12—N1−179.94 (17)
N1—C1—C6—C71.1 (2)C6—C7—C12—N1−0.5 (2)
C2—C1—C6—C7−179.68 (19)C5—C4—C13—O1−8.4 (3)
C5—C6—C7—C8−2.0 (4)C3—C4—C13—O1171.5 (2)
C1—C6—C7—C8179.0 (2)C1—N1—C14—C1586.1 (3)
C5—C6—C7—C12178.6 (2)C12—N1—C14—C15−90.2 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BH2297).

References

  • Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Dijken, A. van, Bastiaansen, J. J. A. M., Kiggen, N. M. M., Langeveld, B. M. W., Rothe, C., Monkman, A., Bach, I., Stössel, P. & Brunner, K. (2004). J. Am. Chem. Soc.126, 7718–7727. [PubMed]
  • Kimura, T., Kai, Y., Yasuoka, N. & Kasai, N. (1985). Bull. Chem. Soc. Jpn, 58, 2268–2271.
  • Li, J., Liu, D., Li, Y., Lee, C.-S., Kwong, H.-L. & Lee, S. (2005). Chem. Mater.17, 1208–1212.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Wang, J. J., Zhang, X., Zhang, B. Q., Wang, G. & Yu, X. Q. (2008). Acta Cryst. E64, o1293. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography