3-(9H-Carbazol-9-yl)-2H-chromen-2-one

Julien Letessier; Dieter Schollmeyer; Heiner Detert

doi:10.1107/S1600536811034660

. 2011 Aug 27;67(Pt 9):o2494. doi: 10.1107/S1600536811034660

3-(9H-Carbazol-9-yl)-2H-chromen-2-one

Julien Letessier ^a, Dieter Schollmeyer ^a, Heiner Detert ^a,^*

PMCID: PMC3200909 PMID: 22059044

Abstract

The title compound, C₂₁H₁₃NO₂, was prepared as an example of a new synthesis of carbazoles from a cyclic dibenzo-iodolium salt via a twofold Pd-catalysed arylation of a primary amine. The two essentially planar π-subsystems [maximum deviations from the mean square plane of 0.038 (2) Å in the carbazole and 0.059 (2) Å in the coumarine unit] open a dihedral angle of 63.05 (4)°. Two molecules form a centrosymmetrical pair connected via π–π interactions between the pyrrole and pyrone rings [centroid–centroid distance = 3.882 (1) Å] and one benzene of the carbazole and the pyrone unit [centroid–centroid distance 3.824 (1) Å]. The lattice is stabilized by C—H⋯O bridging to both coumarin O atoms.

Related literature

For alkaloids based on the carbazole core, see: Kapil (1971 ▶). For information on carbazoles used as electron-rich and rigid units in functional materials for photoconducting, sensing and luminescence purposes, see: Wakim et al. (2004 ▶); Schmitt et al. (2008 ▶). For carbazoles and δ-carbolines using the iodolium salt route, see Letessier (2011 ▶); Letessier et al. (2011 ▶). For the construction of carbazoles and their heteroanalogous derivatives, see: Nissen & Detert (2011 ▶); Dassonneville et al. (2011 ▶); Letessier et al. (2011 ▶). For the synthesis of annulated heterocycles, see: Nemkovich et al. (2009 ▶); Preis et al. (2011 ▶).

Experimental

Crystal data

C₂₁H₁₃NO₂
M _r = 311.32
Monoclinic,
a = 8.9451 (12) Å
b = 11.5412 (7) Å
c = 15.0477 (17) Å
β = 105.871 (12)°
V = 1494.3 (3) Å³
Z = 4
Cu Kα radiation
μ = 0.72 mm⁻¹
T = 193 K
0.50 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971 ▶) T _min = 0.716, T _max = 0.932
2826 measured reflections
2826 independent reflections
2171 reflections with I > 2σ(I)
3 standard reflections every 60 min intensity decay: 5%

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.142
S = 1.04
2826 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811034660/bt5627sup1.cif

e-67-o2494-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034660/bt5627Isup2.hkl

e-67-o2494-Isup2.hkl^{(138.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811034660/bt5627Isup3.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
C15—H15⋯O24ⁱ	0.95	2.43	3.366 (2)	169
C11—H11⋯O22ⁱⁱ	0.95	2.58	3.522 (2)	170

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

Acknowledgments

The authors are grateful to Heinz Kolshorn for invaluable discussions and the NMR spectra.

supplementary crystallographic information

Comment

The title compound was prepared as a part of a project focused on the synthesis of annulated heterocycles, see: Nemkovich et al. (2009); Preis et al. (2011). The Pd-catalyzed transformation of dibenzoiodolium salts to carbazoles constitutes a new access to carbazoles, especially 9-substituted carbazoles see: Letessier (2011). This method complements our toolbox for the construction of carbazoles and its heteroanalogous derivatives, see Nissen & Detert (2011); Dassonneville et al. (2011) and Letessier et al. (2011). Carbazole and coumarine units are essentially planar with maximum deviations from the mean square plane of 0.04Å in the carbazole and 0.06 Å in the coumarine unit. The dihedral angle between the mean planes is 63.1°. Two molecules form a centrosymmetric pair, they are connected viaπ-π interactions between carbazole and coumarin as indicated by the short distances of the centroids of pyrrole and pyrone of 3.88Å and of one benzene of the carbazole and the pyrone of 3.82 Å. The lattice is stabilized by hydrogen bridging to both coumarin oxgen atoms, C11—H11···O22 (2.58 Å) and C15—H15···O24 (2.43 Å).

Experimental

Dibenzo[b,d]iodol-5-ium trifluoromethanesulfonate (471 mg, 1.10 mmol) (Letessier (2011)), Pd₂(dba)₃ (40 mg, 0.044 mmol), Xantphos (76 mg, 0.13 mmol) and Cs₂CO₃ (1.07 g, 3.30 mmol) were dissolved in freshly distilled toluene (12 ml) in a sealed tube under argon atmosphere and stirred for 5 min at room temperature. 3-Amino-2H-chromen-2-one (213 mg, 1.32 mmol) was added and the mixture was stirred overnight at 373 K. The mixture was cooled to room temperature, filtered trough Celite and concentrated. Purification by silica gel chromatography (petrolether:EtOAc=4:1(v:v)) afforded pure 3-(9H-carbazol-9-yl)-2H-chromen-2-one as a white crystalline solid (51 mg, 0.17 mmol, 14%).