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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1635.
Published online 2008 July 31. doi:  10.1107/S1600536808023441
PMCID: PMC2962081

6-Chloro-3,4-di­hydro-9H-carbazol-1(2H)-one

Abstract

The carbazole unit of the title mol­ecule, C12H10ClNO, is not planar. The dihedral angle between the benzene and pyrrole rings is 1.35 (10)°. The cyclo­hexene ring adopts an envelope conformation. In the crystal structure, inter­molecular N—H(...)O hydrogen bonds form centrosymmetric dimers.

Related literature

For a related structure with a non-planar carbazole unit, see: Sridharan et al. (2008 [triangle]).

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Object name is e-64-o1635-scheme1.jpg

Experimental

Crystal data

  • C12H10ClNO
  • M r = 219.66
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1635-efi1.jpg
  • a = 10.4211 (5) Å
  • b = 5.6851 (3) Å
  • c = 17.0824 (10) Å
  • β = 100.239 (6)°
  • V = 995.93 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.35 mm−1
  • T = 200 (2) K
  • 0.58 × 0.18 × 0.11 mm

Data collection

  • Oxford Diffraction R Gemini diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 [triangle]) T min = 0.923, T max = 1.000 (expected range = 0.888–0.962)
  • 10695 measured reflections
  • 3909 independent reflections
  • 1793 reflections with I > 2σ(I)
  • R int = 0.072

Refinement

  • R[F 2 > 2σ(F 2)] = 0.062
  • wR(F 2) = 0.139
  • S = 0.88
  • 3909 reflections
  • 140 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.46 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 [triangle]); data reduction: CrysAlis RED; 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]); software used to prepare material for publication: PLATON (Spek, 2003 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023441/sj2518sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023441/sj2518Isup2.hkl

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

Acknowledgments

MS thanks the UGC, New Delhi, for the award of a research fellowship. KJR acknowledges the UGC, New Delhi, India, for the award of Major Research Project grant No. F.No.31–122/2005. AT thanks the UGC, India, for the award of a Minor Research Project [File No. MRP-2355/06(UGC-SERO), Link No. 2355, 10/01/2007]. RJB acknowledges the NSF–MRI program for funding to purchase the X-ray CCD diffractometer.

supplementary crystallographic information

Comment

Sridharan et al. (2008) have reported the crystal structure of 6-Methoxy-2,3,4,9-tetrahydro-1H-carbazol-1-one, in which the carbazole unit is not planar. The molecular structure of the title compound, with atomic numbering scheme, is shown in Fig. 1. The carbazole unit of the title molecule is not planar. The dihedral angle between the benzene ring and the pyrrole ring is 1.35 (10)°. The cyclohexene ring adopts an envelope conformation. Intermolecular N9—H9···O1 (-x, -y, -z) hydrogen bonds form centrosymmetric dimers in the crystal structure, Fig. 2.

Experimental

A solution of 2-(2-(4-chlorophenyl)hydrazono)cyclohexanone (0.236 g, 0.001 mol) in a mixture of acetic acid (20 ml) and hydrochloric acid (5 ml) was refluxed on an oil bath pre-heated to 398–403 K for 2 h. The contents were then cooled and poured onto cold water with stirring. The brown solid which separated was purified by passing through a column of silica gel and eluting with (95:5 v/v) petroleum ether-ethyl acetate mixture to yield the title compound (0.153 g, 70%). This was recrystallized from ethanol.

Refinement

The crystal used was very weakly diffracting particularly at high Bragg angles. The H atom bonded to N9 was located in a difference Fourier map and refined isotropically. Other H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95–0.99 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 50% probability level. Hydrogen atoms are represented by spheres of arbitrary radius.
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

C12H10ClNOF000 = 456
Mr = 219.66Dx = 1.465 Mg m3
Monoclinic, P21/cMelting point: 475(1) K
Hall symbol: -P 2ybcMo Kα radiation λ = 0.71073 Å
a = 10.4211 (5) ÅCell parameters from 1948 reflections
b = 5.6851 (3) Åθ = 4.6–34.7º
c = 17.0824 (10) ŵ = 0.35 mm1
β = 100.239 (6)ºT = 200 (2) K
V = 995.93 (9) Å3Needle, colourless
Z = 40.58 × 0.18 × 0.11 mm

Data collection

Oxford Diffraction R Gemini diffractometer3909 independent reflections
Radiation source: fine-focus sealed tube1793 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.072
Detector resolution: 10.5081 pixels mm-1θmax = 34.7º
T = 200(2) Kθmin = 4.6º
[var phi] and ω scansh = −16→15
Absorption correction: multi-scan(CrysAlis RED; Oxford Diffraction, 2008)k = −9→9
Tmin = 0.923, Tmax = 1.000l = −27→19
10695 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.062H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.139  w = 1/[σ2(Fo2) + (0.0611P)2] where P = (Fo2 + 2Fc2)/3
S = 0.88(Δ/σ)max = 0.001
3909 reflectionsΔρmax = 0.46 e Å3
140 parametersΔρmin = −0.23 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 > 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
Cl10.51516 (5)0.81197 (10)−0.14449 (3)0.0418 (2)
O1−0.02083 (14)0.1402 (3)0.10672 (9)0.0403 (5)
N90.14769 (15)0.2338 (3)−0.00949 (10)0.0293 (5)
C10.05496 (17)0.3080 (3)0.11410 (11)0.0276 (5)
C20.06417 (19)0.4778 (4)0.18253 (12)0.0340 (6)
C30.1973 (2)0.5983 (4)0.20336 (12)0.0361 (6)
C40.2388 (2)0.7173 (4)0.13273 (12)0.0358 (7)
C4A0.22083 (17)0.5536 (3)0.06315 (11)0.0258 (5)
C4B0.28050 (17)0.5475 (3)−0.00559 (11)0.0251 (5)
C50.36953 (17)0.6955 (3)−0.03472 (12)0.0286 (5)
C60.40706 (18)0.6321 (3)−0.10471 (12)0.0292 (6)
C70.36271 (19)0.4274 (4)−0.14660 (12)0.0337 (6)
C80.27603 (19)0.2811 (4)−0.11885 (12)0.0318 (6)
C8A0.23419 (17)0.3435 (3)−0.04868 (11)0.0260 (5)
C9A0.13871 (17)0.3614 (3)0.05784 (11)0.0253 (5)
H2A−0.003990.599710.169030.0408*
H2B0.046400.392040.229910.0408*
H3A0.263640.479520.225110.0433*
H3B0.193910.716950.245350.0433*
H4A0.331550.764290.146530.0430*
H4B0.186030.860990.118760.0430*
H50.402310.83389−0.006980.0343*
H70.392750.38971−0.194430.0404*
H80.245550.14153−0.146660.0381*
H90.1137 (19)0.107 (4)−0.0230 (12)0.023 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0407 (3)0.0437 (3)0.0464 (3)−0.0017 (2)0.0224 (2)0.0095 (3)
O10.0350 (7)0.0496 (9)0.0389 (8)−0.0151 (7)0.0138 (7)−0.0069 (8)
N90.0308 (8)0.0319 (9)0.0269 (8)−0.0096 (7)0.0095 (7)−0.0062 (8)
C10.0222 (8)0.0333 (10)0.0273 (9)0.0006 (8)0.0046 (7)0.0012 (9)
C20.0336 (10)0.0437 (12)0.0271 (10)−0.0017 (9)0.0119 (9)−0.0023 (10)
C30.0424 (11)0.0397 (12)0.0279 (10)−0.0077 (9)0.0109 (9)−0.0051 (10)
C40.0459 (12)0.0306 (11)0.0333 (11)−0.0057 (9)0.0138 (10)−0.0061 (10)
C4A0.0265 (9)0.0262 (9)0.0250 (9)0.0022 (7)0.0051 (8)0.0012 (9)
C4B0.0255 (8)0.0275 (10)0.0223 (9)0.0020 (7)0.0043 (7)0.0035 (8)
C50.0302 (9)0.0269 (10)0.0294 (9)−0.0009 (8)0.0071 (8)0.0023 (9)
C60.0273 (9)0.0319 (11)0.0305 (10)0.0040 (7)0.0113 (8)0.0085 (9)
C70.0355 (10)0.0412 (12)0.0266 (9)0.0051 (9)0.0117 (9)0.0005 (10)
C80.0344 (10)0.0348 (11)0.0276 (10)−0.0007 (8)0.0097 (8)−0.0046 (9)
C8A0.0244 (8)0.0302 (10)0.0240 (9)0.0004 (7)0.0057 (7)0.0006 (9)
C9A0.0240 (8)0.0287 (10)0.0238 (9)0.0026 (7)0.0056 (7)0.0007 (8)

Geometric parameters (Å, °)

Cl1—C61.7460 (19)C5—C61.371 (3)
O1—C11.231 (2)C6—C71.401 (3)
N9—C8A1.365 (2)C7—C81.373 (3)
N9—C9A1.377 (2)C8—C8A1.392 (3)
N9—H90.82 (2)C2—H2A0.9900
C1—C9A1.441 (3)C2—H2B0.9900
C1—C21.506 (3)C3—H3A0.9900
C2—C31.531 (3)C3—H3B0.9900
C3—C41.512 (3)C4—H4A0.9900
C4—C4A1.495 (3)C4—H4B0.9900
C4A—C4B1.424 (3)C5—H50.9500
C4A—C9A1.381 (2)C7—H70.9500
C4B—C8A1.412 (2)C8—H80.9500
C4B—C51.407 (3)
Cl1···C4Ai3.5299 (19)C8A···H2Avi2.8900
Cl1···H7ii3.1000C9A···H3A3.0000
Cl1···H4Aiii2.8900C9A···H4Bv3.0400
O1···N92.924 (2)H2A···H2Bx2.4900
O1···N9iv2.872 (2)H2A···C8vi2.8900
O1···H4Bv2.6600H2A···C8Avi2.8900
O1···H92.83 (2)H2B···H2Axi2.4900
O1···H9iv2.11 (2)H3A···C9A3.0000
N9···O12.924 (2)H3A···C8vii3.0300
N9···O1iv2.872 (2)H3A···H8vii2.3400
C4A···Cl1i3.5299 (19)H3B···C7xii3.0700
C5···C5i3.549 (3)H4A···Cl1iii2.8900
C5···C6i3.548 (3)H4B···O1xiii2.6600
C6···C5i3.548 (3)H4B···C1xiii2.8800
C9A···C9Avi3.566 (3)H4B···C9Axiii3.0400
C1···H4Bv2.8800H7···Cl1xiv3.1000
C3···H8vii2.8700H8···C3ix2.8700
C7···H3Bviii3.0700H8···H3Aix2.3400
C8···H2Avi2.8900H9···O12.83 (2)
C8···H3Aix3.0300H9···O1iv2.11 (2)
C8A—N9—C9A108.53 (15)C1—C9A—C4A124.38 (17)
C9A—N9—H9127.6 (14)N9—C9A—C1125.83 (16)
C8A—N9—H9123.7 (14)N9—C9A—C4A109.78 (16)
O1—C1—C9A123.29 (17)C1—C2—H2A109.00
O1—C1—C2121.85 (17)C1—C2—H2B109.00
C2—C1—C9A114.85 (16)C3—C2—H2A109.00
C1—C2—C3113.41 (16)C3—C2—H2B109.00
C2—C3—C4112.99 (17)H2A—C2—H2B108.00
C3—C4—C4A110.04 (18)C2—C3—H3A109.00
C4B—C4A—C9A106.44 (16)C2—C3—H3B109.00
C4—C4A—C4B131.28 (17)C4—C3—H3A109.00
C4—C4A—C9A122.24 (17)C4—C3—H3B109.00
C5—C4B—C8A119.51 (17)H3A—C3—H3B108.00
C4A—C4B—C8A106.93 (15)C3—C4—H4A110.00
C4A—C4B—C5133.57 (17)C3—C4—H4B110.00
C4B—C5—C6117.36 (16)C4A—C4—H4A110.00
Cl1—C6—C5119.30 (14)C4A—C4—H4B110.00
Cl1—C6—C7117.70 (15)H4A—C4—H4B108.00
C5—C6—C7123.00 (17)C4B—C5—H5121.00
C6—C7—C8120.30 (19)C6—C5—H5121.00
C7—C8—C8A117.96 (19)C6—C7—H7120.00
N9—C8A—C8129.85 (17)C8—C7—H7120.00
C4B—C8A—C8121.86 (17)C7—C8—H8121.00
N9—C8A—C4B108.29 (16)C8A—C8—H8121.00
C9A—N9—C8A—C4B−0.6 (2)C4—C4A—C4B—C8A175.46 (19)
C9A—N9—C8A—C8179.52 (19)C9A—C4A—C4B—C5178.3 (2)
C8A—N9—C9A—C1178.12 (17)C4B—C4A—C9A—N91.7 (2)
C8A—N9—C9A—C4A−0.7 (2)C4B—C4A—C9A—C1−177.15 (17)
C2—C1—C9A—N9−179.78 (17)C4A—C4B—C8A—N91.6 (2)
C2—C1—C9A—C4A−1.1 (3)C5—C4B—C8A—C81.3 (3)
O1—C1—C2—C3153.79 (19)C4A—C4B—C8A—C8−178.47 (18)
C9A—C1—C2—C3−27.7 (2)C5—C4B—C8A—N9−178.63 (16)
O1—C1—C9A—N9−1.3 (3)C4A—C4B—C5—C6179.7 (2)
O1—C1—C9A—C4A177.38 (18)C8A—C4B—C5—C60.0 (3)
C1—C2—C3—C453.7 (2)C4B—C5—C6—Cl1178.90 (14)
C2—C3—C4—C4A−48.1 (2)C4B—C5—C6—C7−1.2 (3)
C3—C4—C4A—C4B−157.05 (19)Cl1—C6—C7—C8−178.99 (16)
C3—C4—C4A—C9A20.1 (3)C5—C6—C7—C81.1 (3)
C4—C4A—C9A—N9−176.05 (17)C6—C7—C8—C8A0.2 (3)
C4—C4A—C9A—C15.1 (3)C7—C8—C8A—N9178.52 (19)
C9A—C4A—C4B—C8A−2.0 (2)C7—C8—C8A—C4B−1.4 (3)
C4—C4A—C4B—C5−4.2 (4)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, y+1/2, −z−1/2; (iii) −x+1, −y+2, −z; (iv) −x, −y, −z; (v) x, y−1, z; (vi) −x, −y+1, −z; (vii) x, −y+1/2, z+1/2; (viii) x, −y+3/2, z−1/2; (ix) x, −y+1/2, z−1/2; (x) −x, y+1/2, −z+1/2; (xi) −x, y−1/2, −z+1/2; (xii) x, −y+3/2, z+1/2; (xiii) x, y+1, z; (xiv) −x+1, y−1/2, −z−1/2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N9—H9···O1iv0.82 (2)2.11 (2)2.872 (2)154 (2)

Symmetry codes: (iv) −x, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2518).

References

  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.
  • Sridharan, M., Prasad, K. J. R., Gunaseelan, A. T., Thiruvalluvar, A. & Linden, A. (2008). Acta Cryst. E64, o763–o764. [PMC free article] [PubMed]

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