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Acta Cryst. (2008). E64, o1681    [ doi:10.1107/S1600536808024318 ]

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

S. Murugavel, G. Ganesh, A. S. Pandi, R. Murugan and S. S. Narayanan

Abstract top

In the title compound, C28H30N2O2, the cyclohexene ring system adopts a sofa conformation. The crystal structure is stabilized by C-H...O interactions between methyl H atoms of the ethyl substituents and the O atoms of carbonyl groups of adjacent molecules, and by an intermolecular carbonyl-carbonyl interactions [3.207 (2) Å]

Comment top

Carbazole derivatives exhibit good charge transfer and hole transporting properties, which are being explored for a multitude of optoelectronic and photocatalytic applications, including organic light emitting diodes (OLEDs) (Mi et al., 2003). In carbazole derivatives, the preliminary study shows that the presence of oxygenated substituents increases their biological activity (Hewlins, Oliveira-Campos & Shannon, 1984). The 2,3-disubstituted indoles have been used as bidentate synthons for the synthesis of various medicinally important carbazole alkaloids (Mohanakrishnan & Srinivasan, 1995). Intercalation between the base pairs in DNA has been implicated for their anticancer activity. It was conceived that the benzo[b] carbazoles as isosteric analogs of pyrido[4,3-b]carbazoles, with oxygenated D-ring could mimic the anti-cancer activity of ellipticine. So it was of interest to study the anticancer activity of D-ring oxygenated benzo[b]carbazoles as it is believed that these molecules could form a stable intercalation complex with DNA (Kansal & Potier, 1986). Tetrahydrocarbazole derivatives are present in the framework of indole-type alkaloids of biological interest (Phillipson & Zenk, 1980; Saxton, 1983; Abraham, 1975). Here we report the crystal and molecular structure of the title compound, 9-ethyl-1,2,3-trihydrocarbazol-4(2H)-one (Fig. 1).

The planarities of rings A and C are fairly good. The bond lengths C8—O1, N1—C5 and N1—C12 are normal and comparable with the corresponding values observed in the related structure. (Govindasamy et al., 1999). The atom O1 deviates by -0.033 (1) Å from the least-squares plane of the ring C. The cyclohexane ring of the carbazole moiety adopts sofa conformation, with lowest displacement asymmetric parameter (Nardelli, 1983), ΔCs(C7) = 2.26 (1) °, and puckering parameter (Cremer & Popple, 1975) q2 = 0.373 (2) Å and φ = 359.1 (2) °. The crystal packing (Fig. 2) is stabilized by a C—H···O interaction between a methyl H atom of the ethyl substituent and the oxygen of the carbonyl group of an adjacent molecule, with a C14—H14A···O1i separation of 2.60 Å (Fig. 2 and Table 1; symmetry code as in Fig. 2). The molecular packing (Fig. 2) is further stabilized by a type-II carbonyl-carbonyl interaction (Allen et al., 1998), with C8···O1ii and O1···C8ii distance of 3.207 (2) Å (symmetry code as in Fig. 2).

Related literature top

For related literature, see: Abraham (1975); Govindasamy et al. (1999); Hewlins et al. (1984); Kansal et al. (1986); Mi et al. (2003); Nardelli (1983); Phillipson & Zenk (1980); Saxton (1983); Allen et al. (1998); Cremer & Popple (1975); Mohanakrishnan & Srinivasasan (1995, 1995).

Experimental top

A mixture of (0.5 g, 1.0 mol), ethyl bromide (0.18 g, 1.0 mol) and potassium carbonate (2.0 g) in 1,4-dioxane (10 ml) was refluxed for ca. 5.0 h. Then the reaction mixture was poured in water and then the crude solid was filtered. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in ethanol at room temperature.

Refinement top

All H atoms were fixed geometrically and allowed to ride on their parent C atoms, with C—H distances fixed in the range 0.93–0.98 Å with Uiso(H) = 1.5Ueq(C) for methyl H 1.2Ueq(C) for other H atoms.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Ferrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound showing 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. C—H···O and C···O interaction(dotted lines) in the title compound. [Symmetry code: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y+1, -z+2; (iii) x, y, z-1.]
9-Ethyl-2,3-dihydro-9H-carbazol-4(1H)-one top
Crystal data top
C14H15NOF000 = 456
Mr = 213.27Dx = 1.288 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2850 reflections
a = 8.3742 (6) Åθ = 20.0–26.8º
b = 17.033 (1) ŵ = 0.08 mm−1
c = 8.6083 (5) ÅT = 293 (2) K
β = 116.432 (3)ºBlock, colourless
V = 1099.51 (12) Å30.21 × 0.19 × 0.17 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2334 independent reflections
Radiation source: fine-focus sealed tube1898 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
Detector resolution: 10 pixels mm-1θmax = 26.8º
T = 293(2) Kθmin = 2.4º
ω scansh = −10→10
Absorption correction: nonek = −21→21
11070 measured reflectionsl = −10→10
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.105  w = 1/[σ2(Fo2) + (0.0497P)2 + 0.2126P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2334 reflectionsΔρmax = 0.15 e Å−3
146 parametersΔρmin = −0.20 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C14H15NOV = 1099.51 (12) Å3
Mr = 213.27Z = 4
Monoclinic, P21/nMo Kα
a = 8.3742 (6) ŵ = 0.08 mm−1
b = 17.033 (1) ÅT = 293 (2) K
c = 8.6083 (5) Å0.21 × 0.19 × 0.17 mm
β = 116.432 (3)º
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2334 independent reflections
Absorption correction: none1898 reflections with I > 2σ(I)
11070 measured reflectionsRint = 0.029
Refinement top
R[F2 > 2σ(F2)] = 0.040146 parameters
wR(F2) = 0.105H-atom parameters constrained
S = 1.03Δρmax = 0.15 e Å−3
2334 reflectionsΔρmin = −0.20 e Å−3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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) top
xyzUiso*/Ueq
C10.41850 (18)0.62548 (8)0.62150 (18)0.0419 (3)
H10.52000.63880.72170.050*
C20.3279 (2)0.68137 (8)0.4981 (2)0.0506 (4)
H20.36850.73300.51600.061*
C30.1766 (2)0.66211 (9)0.3472 (2)0.0527 (4)
H30.11860.70110.26590.063*
C40.11103 (19)0.58687 (8)0.31534 (17)0.0457 (3)
H40.01020.57410.21400.055*
C50.20092 (16)0.53077 (8)0.44009 (15)0.0359 (3)
C60.35512 (16)0.54847 (7)0.59327 (15)0.0343 (3)
C70.40707 (16)0.47683 (7)0.69054 (15)0.0350 (3)
C80.55752 (16)0.45924 (8)0.85455 (16)0.0392 (3)
C90.56815 (19)0.37540 (9)0.91598 (19)0.0490 (4)
H9A0.62180.37521.04170.059*
H9B0.64620.34610.88110.059*
C100.38967 (19)0.33358 (9)0.84713 (19)0.0509 (4)
H10A0.31780.35740.89700.061*
H10B0.40910.27900.88320.061*
C110.28888 (19)0.33744 (8)0.65050 (19)0.0465 (3)
H11A0.34760.30490.59890.056*
H11B0.16820.31820.61230.056*
C120.28502 (16)0.42042 (7)0.59547 (16)0.0364 (3)
C130.01251 (17)0.41064 (8)0.30768 (17)0.0431 (3)
H13A−0.07910.44830.24000.052*
H13B−0.03880.37400.35930.052*
C140.0697 (2)0.36655 (11)0.1896 (2)0.0595 (4)
H14A0.12500.40220.14180.089*
H14B−0.03260.34290.09730.089*
H14C0.15340.32640.25430.089*
N10.16080 (13)0.45195 (6)0.44527 (13)0.0372 (3)
O10.67261 (13)0.50731 (6)0.93817 (12)0.0530 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0411 (7)0.0438 (7)0.0420 (7)−0.0052 (6)0.0196 (6)−0.0026 (6)
C20.0601 (9)0.0400 (7)0.0568 (9)−0.0026 (7)0.0307 (8)0.0030 (6)
C30.0602 (9)0.0474 (8)0.0506 (8)0.0113 (7)0.0248 (7)0.0144 (7)
C40.0426 (8)0.0533 (8)0.0364 (7)0.0082 (6)0.0134 (6)0.0042 (6)
C50.0341 (6)0.0409 (7)0.0335 (6)0.0027 (5)0.0158 (5)−0.0019 (5)
C60.0321 (6)0.0397 (7)0.0331 (6)0.0006 (5)0.0164 (5)−0.0013 (5)
C70.0314 (6)0.0387 (7)0.0336 (6)0.0000 (5)0.0133 (5)−0.0012 (5)
C80.0312 (6)0.0514 (8)0.0344 (6)0.0007 (6)0.0140 (5)−0.0014 (6)
C90.0422 (8)0.0549 (9)0.0430 (7)0.0080 (6)0.0128 (6)0.0090 (6)
C100.0509 (9)0.0447 (8)0.0546 (8)0.0030 (6)0.0213 (7)0.0113 (6)
C110.0443 (8)0.0370 (7)0.0535 (8)−0.0003 (6)0.0176 (6)−0.0008 (6)
C120.0327 (6)0.0393 (7)0.0362 (6)0.0019 (5)0.0145 (5)−0.0018 (5)
C130.0311 (7)0.0491 (8)0.0415 (7)−0.0042 (6)0.0093 (5)−0.0086 (6)
C140.0462 (9)0.0782 (11)0.0497 (8)−0.0101 (8)0.0172 (7)−0.0251 (8)
N10.0318 (5)0.0389 (6)0.0346 (6)−0.0001 (4)0.0092 (4)−0.0041 (4)
O10.0399 (5)0.0643 (7)0.0420 (5)−0.0092 (5)0.0067 (4)−0.0038 (5)
Geometric parameters (Å, °) top
C1—C21.376 (2)C9—H9A0.9700
C1—C61.395 (2)C9—H9B0.9700
C1—H10.9300C10—C111.520 (2)
C2—C31.391 (2)C10—H10A0.9700
C2—H20.9300C10—H10B0.9700
C3—C41.373 (2)C11—C121.486 (2)
C3—H30.9300C11—H11A0.9700
C4—C51.383 (2)C11—H11B0.9700
C4—H40.9300C12—N11.358 (2)
C5—N11.390 (2)C13—N11.460 (2)
C5—C61.408 (2)C13—C141.503 (2)
C6—C71.434 (2)C13—H13A0.9700
C7—C121.376 (2)C13—H13B0.9700
C7—C81.445 (2)C14—H14A0.9600
C8—O11.225 (2)C14—H14B0.9600
C8—C91.512 (2)C14—H14C0.9600
C9—C101.518 (2)
C2—C1—C6118.67 (13)C9—C10—C11112.13 (12)
C2—C1—H1120.7C9—C10—H10A109.2
C6—C1—H1120.7C11—C10—H10A109.2
C1—C2—C3121.19 (14)C9—C10—H10B109.2
C1—C2—H2119.4C11—C10—H10B109.2
C3—C2—H2119.4H10A—C10—H10B107.9
C4—C3—C2121.57 (13)C12—C11—C10108.58 (11)
C4—C3—H3119.2C12—C11—H11A110.0
C2—C3—H3119.2C10—C11—H11A110.0
C3—C4—C5117.31 (13)C12—C11—H11B110.0
C3—C4—H4121.3C10—C11—H11B110.0
C5—C4—H4121.3H11A—C11—H11B108.4
C4—C5—N1129.54 (12)N1—C12—C7109.97 (11)
C4—C5—C6122.31 (12)N1—C12—C11125.32 (11)
N1—C5—C6108.12 (10)C7—C12—C11124.71 (11)
C1—C6—C5118.94 (12)N1—C13—C14112.16 (11)
C1—C6—C7134.87 (12)N1—C13—H13A109.2
C5—C6—C7106.15 (11)C14—C13—H13A109.2
C12—C7—C6107.16 (11)N1—C13—H13B109.2
C12—C7—C8122.03 (12)C14—C13—H13B109.2
C6—C7—C8130.79 (12)H13A—C13—H13B107.9
O1—C8—C7123.48 (13)C13—C14—H14A109.5
O1—C8—C9121.17 (12)C13—C14—H14B109.5
C7—C8—C9115.32 (11)H14A—C14—H14B109.5
C8—C9—C10114.35 (11)C13—C14—H14C109.5
C8—C9—H9A108.7H14A—C14—H14C109.5
C10—C9—H9A108.7H14B—C14—H14C109.5
C8—C9—H9B108.7C12—N1—C5108.60 (10)
C10—C9—H9B108.7C12—N1—C13126.60 (11)
H9A—C9—H9B107.6C5—N1—C13124.77 (11)
C6—C1—C2—C3−0.4 (2)C7—C8—C9—C10−26.10 (17)
C1—C2—C3—C40.3 (2)C8—C9—C10—C1153.43 (17)
C2—C3—C4—C50.3 (2)C9—C10—C11—C12−50.05 (16)
C3—C4—C5—N1177.12 (13)C6—C7—C12—N10.19 (14)
C3—C4—C5—C6−0.9 (2)C8—C7—C12—N1−178.24 (11)
C2—C1—C6—C5−0.11 (18)C6—C7—C12—C11−179.46 (12)
C2—C1—C6—C7−177.39 (13)C8—C7—C12—C112.1 (2)
C4—C5—C6—C10.80 (18)C10—C11—C12—N1−155.43 (12)
N1—C5—C6—C1−177.59 (11)C10—C11—C12—C724.16 (19)
C4—C5—C6—C7178.79 (12)C7—C12—N1—C50.06 (14)
N1—C5—C6—C70.40 (13)C11—C12—N1—C5179.71 (12)
C1—C6—C7—C12177.16 (14)C7—C12—N1—C13178.10 (11)
C5—C6—C7—C12−0.36 (13)C11—C12—N1—C13−2.2 (2)
C1—C6—C7—C8−4.6 (2)C4—C5—N1—C12−178.53 (13)
C5—C6—C7—C8177.88 (12)C6—C5—N1—C12−0.29 (13)
C12—C7—C8—O1176.58 (12)C4—C5—N1—C133.4 (2)
C6—C7—C8—O1−1.4 (2)C6—C5—N1—C13−178.38 (11)
C12—C7—C8—C9−1.59 (18)C14—C13—N1—C12−80.84 (17)
C6—C7—C8—C9−179.60 (13)C14—C13—N1—C596.90 (16)
O1—C8—C9—C10155.68 (13)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C14—H14A···O1i0.962.603.549 (2)170
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C14—H14A···O1i0.962.603.549 (2)170
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

The authors are greatful to Dr S. Pandi, Head of the Department of Physics, Presidency College (Autonomous), Chennai, for providing the necessary facilities. Dr Babu Varghese, SAIF, IIT, Madras, India, is thanked for collecting the X-ray intensity data.

references
References top

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