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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1136.
Published online 2009 April 25. doi:  10.1107/S1600536809015141
PMCID: PMC2977808

Methyl 9H-carbazole-9-acetate

Abstract

The title compound, C15H13NO2, was synthesized by N-alkyl­ation of methyl bromo­acetate with 9H-carbazole. The carbazole ring system is essentially planar (mean atomic deviation = 0.0346 Å) and makes a dihedral angle of 86.5 (7)° with the methyl acetate group. Weak inter­molecular C—H(...)O hydrogen bonding is present in the crystal structure.

Related literature

The title compound is an inter­mediate in the synthesis of -(9-carbazole) acetyl chloride, a novel fluorescence derivatization reagent, see: Xie et al. (2006 [triangle]); Bong et al. (1992 [triangle]). For bond distances, see: Allen et al. (1987 [triangle]). For the synthesis, see: Xie et al. (2006 [triangle]).

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Object name is e-65-o1136-scheme1.jpg

Experimental

Crystal data

  • C15H13NO2
  • M r = 239.26
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1136-efi1.jpg
  • a = 10.875 (3) Å
  • b = 5.8773 (12) Å
  • c = 18.608 (4) Å
  • β = 103.599 (3)°
  • V = 1155.9 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 93 K
  • 0.43 × 0.33 × 0.27 mm

Data collection

  • Rigaku SPIDER diffractometer
  • Absorption correction: none
  • 8735 measured reflections
  • 2615 independent reflections
  • 1587 reflections with I > 2σ(I)
  • R int = 0.041

Refinement

  • R[F 2 > 2σ(F 2)] = 0.055
  • wR(F 2) = 0.143
  • S = 1.00
  • 2615 reflections
  • 164 parameters
  • H-atom parameters constrained
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: RAPID-AUTO (Rigaku, 2004 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015141/xu2513sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809015141/xu2513Isup2.hkl

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

Acknowledgments

The authors acknowledge financial support from the Jiangsu Institute of Nuclear Medicine, China.

supplementary crystallographic information

Comment

The title compound is useful as an intermediate in the synthesis of 2-(9-carbazole) acetyl chloride, a novel fluorescence derivatization reagent (Xie et al., 2006; Bong et al., 1992). We report here the crystal structure of (I), which is of interest to us in the field. The molecular structure of(I) is showed in Fig.1. The bond lengths and angles are within normal ranges (Allen et al., 1987). The carbazole ring system is essentially planar with mean deviation of 0.0346 Å. The methylacetate substituent adopts a fully extended conformation, and its mean plane forms a dihedral angle of 93.5 (7)° with the carbazole mean plane. In the crystal structure weak C—H···O hydrogen bonding in present (Table 1).

Experimental

The title compound was prepared by the method reported in literature (Xie et al., 2006). The crystals were obtained by dissolving the title compound (0.1 g) in methanol (20 ml), and evaporating the solvent slowly at room temperature. Colorless prism-shaped crystals were formed after 3 d.

Refinement

H atoms were placed in calculated positions and refined in ride mode with C—H = 0.95, 0.99 and 0.98 Å for aromatic, methylene and methyl H atoms. Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

Crystal data

C15H13NO2F(000) = 504
Mr = 239.26Dx = 1.375 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3382 reflections
a = 10.875 (3) Åθ = 3.3–27.5°
b = 5.8773 (12) ŵ = 0.09 mm1
c = 18.608 (4) ÅT = 93 K
β = 103.599 (3)°Prism, colorless
V = 1155.9 (5) Å30.43 × 0.33 × 0.27 mm
Z = 4

Data collection

Rigaku SPIDER diffractometer1587 reflections with I > 2σ(I)
Radiation source: Rotating AnodeRint = 0.041
graphiteθmax = 27.5°, θmin = 3.3°
ω scansh = −14→14
8735 measured reflectionsk = −7→7
2615 independent reflectionsl = −24→20

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)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0306P)2 + 1.86P] where P = (Fo2 + 2Fc2)/3
2615 reflections(Δ/σ)max < 0.001
164 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = −0.36 e Å3

Special details

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 > 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
O10.15039 (15)0.6886 (3)0.49433 (9)0.0250 (4)
O20.11310 (18)1.0517 (3)0.45700 (10)0.0349 (5)
N10.31648 (18)0.7955 (3)0.62011 (11)0.0239 (5)
C10.4231 (2)0.6749 (4)0.61296 (13)0.0242 (5)
C20.5141 (2)0.7323 (4)0.57434 (13)0.0272 (6)
H20.50810.86960.54680.033*
C30.6132 (2)0.5828 (5)0.57759 (13)0.0295 (6)
H30.67670.61910.55200.035*
C40.6228 (2)0.3793 (5)0.61751 (13)0.0290 (6)
H40.69120.27840.61790.035*
C50.5332 (2)0.3246 (4)0.65647 (13)0.0268 (6)
H50.54000.18720.68400.032*
C60.4324 (2)0.4737 (4)0.65483 (13)0.0234 (5)
C70.3267 (2)0.4732 (4)0.68959 (13)0.0237 (5)
C80.2899 (2)0.3290 (4)0.74042 (13)0.0276 (6)
H80.33640.19420.75680.033*
C90.1848 (2)0.3858 (5)0.76644 (14)0.0309 (6)
H90.16020.29140.80210.037*
C100.1143 (2)0.5807 (5)0.74077 (14)0.0304 (6)
H100.04120.61410.75850.036*
C110.1483 (2)0.7260 (5)0.69037 (14)0.0289 (6)
H110.09940.85740.67300.035*
C120.2565 (2)0.6735 (4)0.66592 (13)0.0247 (5)
C130.2590 (2)0.9803 (4)0.57265 (13)0.0263 (6)
H13A0.32731.07130.55970.032*
H13B0.21461.08020.60120.032*
C140.1662 (2)0.9128 (4)0.50173 (13)0.0230 (5)
C150.0599 (2)0.6135 (4)0.42803 (13)0.0284 (6)
H15A−0.02520.66340.43010.034*
H15B0.06170.44710.42500.034*
H15C0.08210.67940.38440.034*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0257 (9)0.0222 (9)0.0240 (9)−0.0003 (7)−0.0001 (7)0.0000 (7)
O20.0394 (11)0.0295 (10)0.0297 (10)0.0044 (8)−0.0043 (8)0.0064 (8)
N10.0227 (10)0.0239 (11)0.0238 (10)0.0030 (8)0.0031 (8)0.0028 (9)
C10.0241 (12)0.0244 (13)0.0217 (12)0.0004 (10)0.0005 (9)−0.0026 (10)
C20.0275 (13)0.0284 (13)0.0236 (12)−0.0001 (11)0.0021 (10)0.0023 (10)
C30.0298 (13)0.0358 (15)0.0233 (12)−0.0010 (11)0.0073 (10)−0.0008 (11)
C40.0246 (12)0.0358 (14)0.0244 (12)0.0034 (11)0.0014 (10)−0.0012 (11)
C50.0253 (12)0.0237 (13)0.0279 (13)0.0033 (10)−0.0006 (10)0.0003 (11)
C60.0232 (12)0.0247 (12)0.0204 (11)0.0005 (10)0.0012 (9)0.0003 (10)
C70.0226 (12)0.0251 (12)0.0204 (11)−0.0018 (10)−0.0007 (9)0.0004 (10)
C80.0273 (13)0.0290 (13)0.0237 (12)−0.0021 (11)0.0001 (10)−0.0008 (11)
C90.0271 (13)0.0361 (15)0.0278 (13)−0.0034 (12)0.0031 (10)0.0010 (12)
C100.0246 (12)0.0402 (16)0.0258 (13)−0.0006 (11)0.0049 (10)−0.0023 (12)
C110.0266 (13)0.0310 (14)0.0268 (13)0.0031 (11)0.0016 (10)−0.0032 (11)
C120.0244 (12)0.0244 (13)0.0226 (12)−0.0010 (10)0.0000 (10)−0.0024 (10)
C130.0281 (13)0.0227 (13)0.0250 (12)0.0032 (10)0.0001 (10)0.0020 (10)
C140.0234 (12)0.0191 (12)0.0266 (12)0.0016 (10)0.0059 (10)−0.0003 (10)
C150.0258 (12)0.0310 (13)0.0249 (12)−0.0038 (11)−0.0010 (10)−0.0034 (11)

Geometric parameters (Å, °)

O1—C141.332 (3)C7—C81.397 (3)
O1—C151.454 (3)C7—C121.416 (3)
O2—C141.211 (3)C8—C91.383 (3)
N1—C121.388 (3)C8—H80.9500
N1—C11.392 (3)C9—C101.399 (4)
N1—C131.446 (3)C9—H90.9500
C1—C21.394 (3)C10—C111.381 (4)
C1—C61.407 (3)C10—H100.9500
C2—C31.381 (4)C11—C121.393 (3)
C2—H20.9500C11—H110.9500
C3—C41.398 (4)C13—C141.514 (3)
C3—H30.9500C13—H13A0.9900
C4—C51.383 (3)C13—H13B0.9900
C4—H40.9500C15—H15A0.9800
C5—C61.398 (3)C15—H15B0.9800
C5—H50.9500C15—H15C0.9800
C6—C71.445 (3)
C14—O1—C15115.67 (18)C8—C9—C10120.7 (2)
C12—N1—C1108.52 (19)C8—C9—H9119.7
C12—N1—C13124.4 (2)C10—C9—H9119.7
C1—N1—C13125.0 (2)C11—C10—C9121.7 (2)
N1—C1—C2129.4 (2)C11—C10—H10119.1
N1—C1—C6109.1 (2)C9—C10—H10119.1
C2—C1—C6121.5 (2)C10—C11—C12117.8 (2)
C3—C2—C1117.7 (2)C10—C11—H11121.1
C3—C2—H2121.2C12—C11—H11121.1
C1—C2—H2121.2N1—C12—C11129.9 (2)
C2—C3—C4121.8 (2)N1—C12—C7108.9 (2)
C2—C3—H3119.1C11—C12—C7121.2 (2)
C4—C3—H3119.1N1—C13—C14116.1 (2)
C5—C4—C3120.2 (2)N1—C13—H13A108.3
C5—C4—H4119.9C14—C13—H13A108.3
C3—C4—H4119.9N1—C13—H13B108.3
C4—C5—C6119.3 (2)C14—C13—H13B108.3
C4—C5—H5120.4H13A—C13—H13B107.4
C6—C5—H5120.4O2—C14—O1124.5 (2)
C5—C6—C1119.5 (2)O2—C14—C13122.4 (2)
C5—C6—C7133.7 (2)O1—C14—C13113.1 (2)
C1—C6—C7106.8 (2)O1—C15—H15A109.5
C8—C7—C12119.8 (2)O1—C15—H15B109.5
C8—C7—C6133.5 (2)H15A—C15—H15B109.5
C12—C7—C6106.6 (2)O1—C15—H15C109.5
C9—C8—C7118.8 (2)H15A—C15—H15C109.5
C9—C8—H8120.6H15B—C15—H15C109.5
C7—C8—H8120.6
C12—N1—C1—C2−178.1 (2)C6—C7—C8—C9176.1 (3)
C13—N1—C1—C217.5 (4)C7—C8—C9—C101.8 (4)
C12—N1—C1—C6−0.3 (3)C8—C9—C10—C11−1.6 (4)
C13—N1—C1—C6−164.7 (2)C9—C10—C11—C12−0.5 (4)
N1—C1—C2—C3178.6 (2)C1—N1—C12—C11178.8 (2)
C6—C1—C2—C31.0 (4)C13—N1—C12—C11−16.7 (4)
C1—C2—C3—C40.5 (4)C1—N1—C12—C71.0 (3)
C2—C3—C4—C5−1.3 (4)C13—N1—C12—C7165.5 (2)
C3—C4—C5—C60.6 (4)C10—C11—C12—N1−175.1 (2)
C4—C5—C6—C10.8 (4)C10—C11—C12—C72.5 (4)
C4—C5—C6—C7−178.1 (2)C8—C7—C12—N1175.7 (2)
N1—C1—C6—C5−179.7 (2)C6—C7—C12—N1−1.2 (3)
C2—C1—C6—C5−1.6 (4)C8—C7—C12—C11−2.3 (3)
N1—C1—C6—C7−0.5 (3)C6—C7—C12—C11−179.3 (2)
C2—C1—C6—C7177.6 (2)C12—N1—C13—C14−77.4 (3)
C5—C6—C7—C83.7 (5)C1—N1—C13—C1484.6 (3)
C1—C6—C7—C8−175.3 (3)C15—O1—C14—O2−1.6 (4)
C5—C6—C7—C12−180.0 (3)C15—O1—C14—C13178.6 (2)
C1—C6—C7—C121.0 (3)N1—C13—C14—O2−179.0 (2)
C12—C7—C8—C90.2 (3)N1—C13—C14—O10.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C15—H15B···O2i0.982.433.374 (3)161

Symmetry codes: (i) x, y−1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2513).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bong, Y. Ch., Duck, J. B., Jung, J. J. & Seung, D. L. (1992). Korean J. Chem. Soc.36, 603–605.
  • Rigaku (2004). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Xie, M. H., Qiu, A. Y., He, Y. J., Wu, J., Zhou, X. Q., Zou, P., Liu, Y. L. & Luo, S. N. (2006). Chin. J. Anal. Chem.34, S131–134.

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