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Acta Crystallogr Sect E Struct Rep Online. 2010 December 1; 66(Pt 12): o3198.
Published online 2010 November 17. doi:  10.1107/S1600536810046714
PMCID: PMC3011405

(E)-6-Chloro-2-(furan-2-yl­methyl­idene)-2,3,4,9-tetra­hydro-1H-carbazol-1-one

Abstract

In the title compound, C17H12ClNO2, the carbazole unit is nearly planar [maximum deviation = 0.052 (1) Å]. The pyrrole ring makes dihedral angles of 1.92 (8) and 4.71 (11)° with the benzene and furan rings, respectively. Inter­molecular N—H(...)O hydrogen bonds form R 2 2(10) rings in the crystal structure.

Related literature

For the pharmaceutical inter­est of heteroaryl annulated derivatives of carbazoles, see: Knölker & Reddy (2002 [triangle], 2008 [triangle]). For the preparation of various hetero-annulated carbazoles, see: Sridharan et al. (2008 [triangle]); Danish & Rajendra Prasad (2004 [triangle], 2005 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]).

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Object name is e-66-o3198-scheme1.jpg

Experimental

Crystal data

  • C17H12ClNO2
  • M r = 297.73
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o3198-efi1.jpg
  • a = 15.0985 (2) Å
  • b = 6.1553 (1) Å
  • c = 15.3887 (2) Å
  • β = 104.319 (1)°
  • V = 1385.73 (3) Å3
  • Z = 4
  • Cu Kα radiation
  • μ = 2.47 mm−1
  • T = 295 K
  • 0.48 × 0.34 × 0.12 mm

Data collection

  • Oxford Diffraction Xcalibur Ruby Gemini diffractometer
  • Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 [triangle]) T min = 0.389, T max = 1.000
  • 8660 measured reflections
  • 2834 independent reflections
  • 2676 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.139
  • S = 1.10
  • 2834 reflections
  • 194 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 [triangle]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810046714/bq2253sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046714/bq2253Isup2.hkl

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

Acknowledgments

RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

Aryl and heteroarylcarbazoles are important classes of biologically active compounds that include notable alkaloids of pharmaceutical interest (Knölker & Reddy (2002, 2008)) and heteroaryl annulated derivatives of carbazole. From our laboratory, we have reported the synthesis of 2-benzylidene-2,3,4,9-tetrahydrocarbazoles from the precursors of the 2,3,4,9-tetrahydro-1H-carbazol-1-one type and these synthons were utilized to prepare many heteroannulated carbazoles (Sridharan et al., (2008); Danish & Rajendra Prasad (2004, 2005)).

In the title molecule (Fig. 1), C17H12ClNO2, the carbazole unit is nearly planar [maximum deviation = 0.052 (1) Å for C1]. The pyrrole ring makes dihedral angles of 1.92 (8)° and 4.71 (11)° with the benzene and the furan rings, respectively. Intermolecular N9—H9···O1 hydrogen bonds form a R22(10) (Bernstein et al., 1995) ring in the crystal structure (Table 1, Fig. 2).

Experimental

An equimolar mixture of 6-chloro-2,3,4,9-tetrahydro-1H-carbazol-1-one (1.095 g, 0.005 mol) and furan-2-carbaldehyde (0.41 ml, 0.005 mol) was treated with 25 ml of a 5% ethanolic potassium hydroxide solution and stirred for 6 h at room temperature. The product precipitated as a yellow crystalline mass, was filtered off and washed with 50% ethanol. A further crop of condensation product was obtained on neutralization with acetic acid and dilution with water. The product was recrystallized from methanol to yield 90% (1.336 g) of the title compound. The pure compound was recrystallized from EtOAc.

Refinement

The H atom bonded to N9 was located in a difference Fourier map and refined freely. Other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2Ueq(parent atom).

Figures

Fig. 1.
The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
The molecular packing of the title compound, viewed down the b axis. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.

Crystal data

C17H12ClNO2F(000) = 616
Mr = 297.73Dx = 1.427 Mg m3
Monoclinic, P21/cMelting point: 501 K
Hall symbol: -P 2ybcCu Kα radiation, λ = 1.54184 Å
a = 15.0985 (2) ÅCell parameters from 6923 reflections
b = 6.1553 (1) Åθ = 4.7–75.4°
c = 15.3887 (2) ŵ = 2.47 mm1
β = 104.319 (1)°T = 295 K
V = 1385.73 (3) Å3Prism, pale-yellow
Z = 40.48 × 0.34 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer2834 independent reflections
Radiation source: Enhance (Cu) X-ray Source2676 reflections with I > 2σ(I)
graphiteRint = 0.026
Detector resolution: 10.5081 pixels mm-1θmax = 75.6°, θmin = 5.9°
ω scansh = −18→18
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)k = −5→7
Tmin = 0.389, Tmax = 1.000l = −19→18
8660 measured reflections

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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 1.10w = 1/[σ2(Fo2) + (0.0845P)2 + 0.264P] where P = (Fo2 + 2Fc2)/3
2834 reflections(Δ/σ)max = 0.001
194 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.28 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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 > 2σ(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
Cl6−0.40900 (3)0.76934 (9)0.02641 (5)0.0804 (2)
O10.10076 (8)0.13185 (18)0.07979 (8)0.0510 (3)
O110.38257 (9)0.4505 (3)0.24198 (10)0.0751 (5)
N9−0.09205 (9)0.2203 (2)0.03653 (8)0.0441 (4)
C10.07175 (10)0.2982 (2)0.10858 (9)0.0376 (4)
C20.13341 (10)0.4564 (2)0.16694 (8)0.0383 (4)
C30.09534 (11)0.6580 (2)0.20028 (10)0.0457 (4)
C4−0.00564 (12)0.7036 (3)0.17066 (13)0.0560 (5)
C4A−0.06155 (10)0.5338 (2)0.11436 (8)0.0373 (4)
C4B−0.15750 (10)0.5216 (2)0.07663 (9)0.0394 (4)
C5−0.23081 (11)0.6625 (3)0.07672 (10)0.0476 (5)
C6−0.31602 (11)0.5984 (3)0.02964 (12)0.0535 (5)
C7−0.33227 (11)0.3997 (3)−0.01636 (12)0.0559 (5)
C8−0.26184 (12)0.2604 (3)−0.01737 (11)0.0524 (5)
C8A−0.17369 (10)0.3230 (3)0.02874 (9)0.0420 (4)
C9A−0.02410 (10)0.3493 (2)0.08760 (8)0.0374 (4)
C100.22300 (11)0.4106 (3)0.18622 (10)0.0463 (4)
C120.44470 (14)0.5930 (5)0.28938 (17)0.0812 (8)
C130.40378 (15)0.7606 (4)0.31507 (16)0.0731 (7)
C140.30864 (14)0.7275 (3)0.28188 (14)0.0621 (6)
C150.29763 (11)0.5361 (3)0.23740 (10)0.0496 (5)
H3A0.126890.781950.183100.0548*
H3B0.111730.652440.265290.0548*
H4A−0.014360.839060.137420.0672*
H4B−0.028550.724420.223660.0672*
H5−0.221780.793800.107520.0571*
H7−0.391590.36229−0.046500.0671*
H8−0.272260.12849−0.047690.0629*
H9−0.0853 (14)0.102 (4)0.0073 (14)0.060 (5)*
H100.238670.280200.163360.0556*
H120.507730.574470.301940.0974*
H130.431900.878460.348650.0877*
H140.262370.820100.289280.0746*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl60.0463 (3)0.0751 (4)0.1142 (5)0.0130 (2)0.0090 (3)0.0023 (3)
O10.0491 (6)0.0413 (6)0.0619 (6)0.0001 (4)0.0123 (5)−0.0157 (5)
O110.0436 (7)0.0848 (10)0.0917 (10)0.0015 (6)0.0071 (6)−0.0262 (8)
N90.0461 (7)0.0415 (6)0.0439 (6)−0.0039 (5)0.0094 (5)−0.0113 (5)
C10.0457 (8)0.0334 (6)0.0347 (6)−0.0031 (5)0.0121 (5)−0.0023 (5)
C20.0441 (7)0.0355 (7)0.0357 (6)−0.0033 (5)0.0106 (5)−0.0015 (5)
C30.0483 (8)0.0383 (7)0.0485 (8)−0.0044 (6)0.0084 (6)−0.0116 (6)
C40.0495 (9)0.0438 (8)0.0696 (10)0.0021 (7)0.0049 (8)−0.0228 (7)
C4A0.0427 (7)0.0362 (7)0.0326 (6)−0.0011 (5)0.0088 (5)0.0002 (5)
C4B0.0432 (7)0.0401 (7)0.0348 (6)−0.0018 (5)0.0094 (5)0.0009 (5)
C50.0476 (8)0.0445 (8)0.0502 (8)0.0019 (6)0.0113 (6)−0.0001 (6)
C60.0438 (8)0.0574 (9)0.0578 (9)0.0045 (7)0.0097 (7)0.0074 (7)
C70.0424 (8)0.0650 (10)0.0563 (9)−0.0074 (7)0.0044 (7)−0.0001 (8)
C80.0491 (9)0.0553 (9)0.0501 (8)−0.0104 (7)0.0070 (7)−0.0082 (7)
C8A0.0445 (8)0.0439 (7)0.0372 (6)−0.0037 (6)0.0093 (5)−0.0017 (5)
C9A0.0449 (7)0.0358 (7)0.0316 (6)−0.0045 (5)0.0094 (5)−0.0030 (5)
C100.0467 (8)0.0452 (8)0.0473 (7)−0.0023 (6)0.0120 (6)−0.0080 (6)
C120.0431 (9)0.1089 (19)0.0868 (14)−0.0143 (11)0.0071 (9)−0.0239 (14)
C130.0570 (11)0.0854 (14)0.0749 (12)−0.0234 (10)0.0127 (9)−0.0238 (11)
C140.0527 (10)0.0670 (11)0.0673 (10)−0.0102 (8)0.0160 (8)−0.0205 (9)
C150.0418 (8)0.0585 (9)0.0484 (8)−0.0023 (7)0.0112 (6)−0.0053 (7)

Geometric parameters (Å, °)

Cl6—C61.7452 (18)C6—C71.404 (3)
O1—C11.2380 (17)C7—C81.369 (3)
O11—C121.358 (3)C8—C8A1.399 (2)
O11—C151.372 (2)C10—C151.431 (2)
N9—C8A1.364 (2)C12—C131.313 (4)
N9—C9A1.3791 (19)C13—C141.415 (3)
N9—H90.88 (2)C14—C151.352 (3)
C1—C9A1.438 (2)C3—H3A0.9700
C1—C21.4859 (19)C3—H3B0.9700
C2—C31.5098 (19)C4—H4A0.9700
C2—C101.341 (2)C4—H4B0.9700
C3—C41.506 (3)C5—H50.9300
C4—C4A1.481 (2)C7—H70.9300
C4A—C4B1.423 (2)C8—H80.9300
C4A—C9A1.3763 (18)C10—H100.9300
C4B—C8A1.417 (2)C12—H120.9300
C4B—C51.407 (2)C13—H130.9300
C5—C61.369 (2)C14—H140.9300
Cl6···C12i3.613 (3)C3···H142.7400
O1···N92.8733 (19)C5···H14v3.0700
O1···N9ii2.7935 (17)C9A···H4Bv2.9200
O1···H3Aiii2.6500C14···H3A2.8100
O1···H92.76 (2)C14···H3B2.9600
O1···H102.3400C15···H3B3.0300
O1···H4Aiii2.8000C15···H3A2.9300
O1···H9ii1.94 (2)H3A···O1vi2.6500
N9···O12.8733 (19)H3A···C142.8100
N9···O1ii2.7935 (17)H3A···C152.9300
N9···H4Aiii2.9000H3A···H142.2900
C1···C4Aiv3.5499 (18)H3B···C142.9600
C1···C4Biv3.585 (2)H3B···C153.0300
C2···C8Aiv3.4910 (19)H3B···H142.4400
C3···C143.183 (3)H4A···O1vi2.8000
C4A···C1iv3.5499 (18)H4A···N9vi2.9000
C4B···C1iv3.585 (2)H4A···H9vi2.5900
C7···C15iv3.589 (2)H4B···C1i2.8500
C8···C10iv3.457 (2)H4B···C2i2.9500
C8···C15iv3.524 (2)H4B···C9Ai2.9200
C8A···C2iv3.4910 (19)H9···O12.76 (2)
C9A···C9Aiv3.4944 (18)H9···H4Aiii2.5900
C10···C8iv3.457 (2)H9···O1ii1.94 (2)
C12···Cl6v3.613 (3)H9···C1ii3.08 (2)
C14···C33.183 (3)H10···O12.3400
C15···C8iv3.524 (2)H14···C32.7400
C15···C7iv3.589 (2)H14···H3A2.2900
C1···H4Bv2.8500H14···H3B2.4400
C1···H9ii3.08 (2)H14···C5i3.0700
C2···H4Bv2.9500
C12—O11—C15107.00 (18)O11—C12—C13110.8 (2)
C8A—N9—C9A108.18 (12)C12—C13—C14106.8 (2)
C9A—N9—H9127.4 (14)C13—C14—C15107.15 (18)
C8A—N9—H9123.9 (14)C10—C15—C14136.93 (18)
O1—C1—C9A121.75 (13)O11—C15—C10114.82 (16)
O1—C1—C2122.28 (14)O11—C15—C14108.20 (16)
C2—C1—C9A115.97 (11)C2—C3—H3A107.00
C3—C2—C10123.06 (13)C2—C3—H3B107.00
C1—C2—C3120.65 (13)C4—C3—H3A107.00
C1—C2—C10116.28 (13)C4—C3—H3B107.00
C2—C3—C4119.50 (13)H3A—C3—H3B107.00
C3—C4—C4A115.69 (14)C3—C4—H4A108.00
C4B—C4A—C9A106.65 (11)C3—C4—H4B108.00
C4—C4A—C4B130.64 (13)C4A—C4—H4A108.00
C4—C4A—C9A122.71 (14)C4A—C4—H4B108.00
C5—C4B—C8A119.86 (14)H4A—C4—H4B107.00
C4A—C4B—C5133.55 (13)C4B—C5—H5121.00
C4A—C4B—C8A106.56 (12)C6—C5—H5121.00
C4B—C5—C6117.29 (16)C6—C7—H7120.00
C5—C6—C7122.82 (16)C8—C7—H7120.00
Cl6—C6—C5119.03 (14)C7—C8—H8121.00
Cl6—C6—C7118.15 (13)C8A—C8—H8121.00
C6—C7—C8120.79 (16)C2—C10—H10116.00
C7—C8—C8A117.78 (16)C15—C10—H10116.00
N9—C8A—C8130.00 (16)O11—C12—H12125.00
C4B—C8A—C8121.44 (15)C13—C12—H12125.00
N9—C8A—C4B108.55 (13)C12—C13—H13127.00
C1—C9A—C4A125.36 (12)C14—C13—H13127.00
N9—C9A—C1124.59 (12)C13—C14—H14126.00
N9—C9A—C4A110.05 (13)C15—C14—H14126.00
C2—C10—C15128.47 (16)
C15—O11—C12—C130.5 (3)C9A—C4A—C4B—C8A0.88 (15)
C12—O11—C15—C10177.58 (17)C4—C4A—C9A—N9179.63 (13)
C12—O11—C15—C14−0.2 (2)C4—C4A—C9A—C1−1.0 (2)
C9A—N9—C8A—C4B−0.48 (16)C4B—C4A—C9A—N9−1.21 (15)
C9A—N9—C8A—C8178.81 (16)C4B—C4A—C9A—C1178.14 (12)
C8A—N9—C9A—C1−178.29 (13)C4A—C4B—C5—C6177.85 (15)
C8A—N9—C9A—C4A1.07 (15)C8A—C4B—C5—C60.2 (2)
O1—C1—C2—C3179.69 (13)C4A—C4B—C8A—N9−0.25 (16)
O1—C1—C2—C100.7 (2)C4A—C4B—C8A—C8−179.62 (14)
C9A—C1—C2—C3−0.52 (18)C5—C4B—C8A—N9177.96 (13)
C9A—C1—C2—C10−179.50 (13)C5—C4B—C8A—C8−1.4 (2)
O1—C1—C9A—N91.5 (2)C4B—C5—C6—Cl6−179.12 (12)
O1—C1—C9A—C4A−177.73 (13)C4B—C5—C6—C71.1 (3)
C2—C1—C9A—N9−178.27 (12)Cl6—C6—C7—C8179.00 (14)
C2—C1—C9A—C4A2.48 (19)C5—C6—C7—C8−1.2 (3)
C1—C2—C3—C4−2.7 (2)C6—C7—C8—C8A−0.1 (3)
C10—C2—C3—C4176.20 (15)C7—C8—C8A—N9−177.91 (16)
C1—C2—C10—C15177.45 (15)C7—C8—C8A—C4B1.3 (2)
C3—C2—C10—C15−1.5 (2)C2—C10—C15—O11−177.11 (16)
C2—C3—C4—C4A4.0 (2)C2—C10—C15—C14−0.1 (3)
C3—C4—C4A—C4B178.72 (14)O11—C12—C13—C14−0.5 (3)
C3—C4—C4A—C9A−2.3 (2)C12—C13—C14—C150.4 (3)
C4—C4A—C4B—C52.1 (3)C13—C14—C15—O11−0.1 (2)
C4—C4A—C4B—C8A179.97 (15)C13—C14—C15—C10−177.2 (2)
C9A—C4A—C4B—C5−176.98 (15)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, −y, −z; (iii) x, y−1, z; (iv) −x, −y+1, −z; (v) −x, y−1/2, −z+1/2; (vi) x, y+1, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N9—H9···O1ii0.88 (2)1.94 (2)2.7935 (17)164 (2)

Symmetry codes: (ii) −x, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BQ2253).

References

  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Danish, I. A. & Rajendra Prasad, K. J. (2004). Indian J. Chem. Sect. B, 43, 618–623.
  • Danish, I. A. & Rajendra Prasad, K. J. (2005). Collect. Czech. Chem. Commun.70, 223–236.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Knölker, H. J. & Reddy, K. R. (2002). Chem. Rev.102, 4303–4428. [PubMed]
  • Knölker, H. J. & Reddy, K. R. (2008). The Alkaloids, edited by G. A. Cordell, Vol. 65, pp. 1–430. Amsterdam: Academic Press.
  • Oxford Diffraction (2010). CrysAlis PRO Oxford Diffraction Ltd, Yarnton, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Sridharan, M., Beagle, L. K., Zeller, M. & Rajendra Prasad, K. J. (2008). J. Chem. Res. pp. 572–577.

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