Literature DB >> 21583627

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

A Thomas Gunaseelan, K Prabakaran, K J Rajendra Prasad, A Thiruvalluvar, R J Butcher.   

Abstract

In the title mol-ecule, C(13)H(13)NO, the dihedral angle between the benzene ring and the fused pyrrole ring is 2.03 (5)°. The methyl group at the 3-position has an equatorial orientation. The cyclo-hexene ring adopts an envelope conformation. Three C atoms of the cyclo-hexene ring, with their attached H atoms, and all atoms of the methyl group are disordered over two positions, the site-occupancy factors being 0.883 (2) and 0.117 (2). In the crystal structure, mol-ecules are stabilized by inter-molecular N-H⋯O hydrogen bonds. A C-H⋯π inter-action, involving the benzene ring, is also found.

Entities:  

Year:  2009        PMID： 21583627      PMCID： PMC2977477          DOI： 10.1107/S1600536809028050

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For the biological activity of substituted 2,3,4,9-tetra­hydro­carbazoles, see: Mooradian et al. (1977 ▶); Jean et al. (2004 ▶); Biere et al. (1973 ▶); Lacoume (1973 ▶). For carbazole alkaloids, such as clausenapin, murrayafoline-A, murrayafoline-B, murrayastine, murrayaquinone-A, with a methyl substituent at the C-3 position, see: Knolker & Reddy (2002 ▶). For the preparation of 1-oxo compounds via their corresponding hydrazones, see: Sowmithran & Rajendra Prasad (1986 ▶); Rajendra Prasad & Vijayalakshmi (1994 ▶); Gunaseelan et al. (2007a ▶,b ▶); Sridharan et al. (2008 ▶); Thiruvalluvar et al. (2007 ▶).

Experimental

Crystal data

C13H13NO M = 199.24 Triclinic, a = 5.8301 (3) Å b = 8.4348 (5) Å c = 10.8000 (7) Å α = 78.094 (5)° β = 75.942 (5)° γ = 87.166 (5)° V = 504.11 (5) Å3 Z = 2 Mo Kα radiation μ = 0.08 mm−1 T = 110 K 0.54 × 0.14 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Ruby diffractometer Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 ▶) T min = 0.753, T max = 1.000 (expected range = 0.747–0.992) 5927 measured reflections 3292 independent reflections 2400 reflections with I > 2σ(I) R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.053 wR(F 2) = 0.153 S = 1.00 3292 reflections 144 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.50 e Å−3 Δρmin = −0.27 e Å−3 Data collection: CrysAlis Pro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶). Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028050/wn2337sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028050/wn2337Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C13H13NOZ = 2
Mr = 199.24F(000) = 212
Triclinic, P1Dx = 1.313 Mg m−3
Hall symbol: -P 1Melting point: 462 K
a = 5.8301 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.4348 (5) ÅCell parameters from 2953 reflections
c = 10.8000 (7) Åθ = 4.9–32.7°
α = 78.094 (5)°µ = 0.08 mm−1
β = 75.942 (5)°T = 110 K
γ = 87.166 (5)°Needle, pale-yellow
V = 504.11 (5) Å30.54 × 0.14 × 0.10 mm
Oxford Diffraction Xcalibur Ruby diffractometer3292 independent reflections
Radiation source: fine-focus sealed tube2400 reflections with I > 2σ(I)
graphiteRint = 0.028
Detector resolution: 10.5081 pixels mm-1θmax = 32.7°, θmin = 4.9°
ω scansh = −7→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)k = −10→12
Tmin = 0.753, Tmax = 1.000l = −13→15
5927 measured reflections
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153H atoms treated by a mixture of independent and constrained refinement
S = 1.00w = 1/[σ2(Fo2) + (0.1015P)2] where P = (Fo2 + 2Fc2)/3
3292 reflections(Δ/σ)max = 0.001
144 parametersΔρmax = 0.50 e Å−3
0 restraintsΔρmin = −0.27 e Å−3
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.
xyzUiso*/UeqOcc. (<1)
O1−0.36537 (13)0.49067 (9)0.31075 (7)0.0255 (2)
N9−0.24180 (15)0.34526 (10)0.55707 (8)0.0202 (2)
C1−0.18847 (17)0.40400 (12)0.31405 (9)0.0202 (2)
C2A−0.03045 (19)0.36084 (14)0.19199 (10)0.0265 (3)0.883 (2)
C3A0.22713 (19)0.32688 (14)0.19735 (10)0.0199 (3)0.883 (2)
C4A0.24963 (17)0.20104 (12)0.31810 (9)0.0202 (2)0.883 (2)
C4C0.08447 (16)0.24013 (11)0.43740 (9)0.0179 (2)
C4D0.09067 (17)0.19671 (11)0.57178 (9)0.0189 (2)
C50.25223 (18)0.11247 (12)0.63950 (10)0.0237 (3)
C60.2021 (2)0.09443 (13)0.77313 (10)0.0279 (3)
C7−0.0090 (2)0.15661 (13)0.84233 (10)0.0275 (3)
C8−0.17079 (19)0.24034 (12)0.77927 (10)0.0237 (3)
C8A−0.11770 (17)0.26304 (11)0.64282 (9)0.0190 (2)
C9A−0.11878 (16)0.33125 (11)0.43268 (9)0.0184 (2)
C13A0.3667 (2)0.27429 (16)0.07206 (11)0.0331 (3)0.883 (2)
C4B0.24963 (17)0.20104 (12)0.31810 (9)0.0202 (2)0.117 (2)
C13B0.3667 (2)0.27429 (16)0.07206 (11)0.0331 (3)0.117 (2)
C2B−0.03045 (19)0.36084 (14)0.19199 (10)0.0265 (3)0.117 (2)
C3B0.1473 (15)0.2369 (11)0.1984 (8)0.0199 (3)0.117 (2)
H3A0.298060.430370.202080.0239*0.883 (2)
H50.393310.068820.593920.0285*
H4A0.414240.199600.327910.0243*0.883 (2)
H4B0.212480.092110.307410.0243*0.883 (2)
H8−0.312860.281150.826350.0285*
H9−0.379 (3)0.4111 (17)0.5785 (14)0.041 (4)*
H13A0.352210.35751−0.003720.0496*0.883 (2)
H13B0.533650.260310.074180.0496*0.883 (2)
H13C0.303070.171550.065910.0496*0.883 (2)
H60.311340.039270.819530.0335*
H7−0.040110.140270.934580.0329*
H2A−0.096340.263830.174800.0318*0.883 (2)
H2B−0.034560.451040.117610.0318*0.883 (2)
H2C0.051340.461620.139690.0318*0.117 (2)
H2D−0.135500.329860.141350.0318*0.117 (2)
H3B0.073010.134100.194840.0239*0.117 (2)
H4C0.396910.264400.299330.0243*0.117 (2)
H4D0.291600.084750.335720.0243*0.117 (2)
H13D0.306710.29814−0.007070.0496*0.117 (2)
H13E0.455470.367810.076480.0496*0.117 (2)
H13F0.470890.179580.070160.0496*0.117 (2)
U11U22U33U12U13U23
O10.0174 (3)0.0308 (4)0.0286 (4)0.0122 (3)−0.0071 (3)−0.0076 (3)
N90.0155 (3)0.0238 (4)0.0195 (4)0.0088 (3)−0.0018 (3)−0.0049 (3)
C10.0136 (4)0.0234 (4)0.0237 (4)0.0058 (3)−0.0045 (3)−0.0065 (3)
C2A0.0206 (5)0.0381 (6)0.0213 (4)0.0140 (4)−0.0068 (3)−0.0085 (4)
C3A0.0151 (5)0.0232 (5)0.0196 (5)0.0072 (4)−0.0028 (4)−0.0034 (4)
C4A0.0146 (4)0.0234 (4)0.0213 (4)0.0075 (3)−0.0025 (3)−0.0052 (3)
C4C0.0137 (4)0.0182 (4)0.0200 (4)0.0056 (3)−0.0018 (3)−0.0039 (3)
C4D0.0160 (4)0.0182 (4)0.0207 (4)0.0056 (3)−0.0021 (3)−0.0037 (3)
C50.0204 (5)0.0239 (5)0.0247 (5)0.0107 (4)−0.0045 (4)−0.0036 (4)
C60.0289 (5)0.0291 (5)0.0240 (5)0.0128 (4)−0.0087 (4)−0.0018 (4)
C70.0318 (5)0.0266 (5)0.0205 (5)0.0095 (4)−0.0042 (4)−0.0016 (4)
C80.0236 (5)0.0231 (4)0.0209 (4)0.0064 (4)0.0000 (3)−0.0041 (4)
C8A0.0165 (4)0.0176 (4)0.0209 (4)0.0051 (3)−0.0021 (3)−0.0033 (3)
C9A0.0135 (4)0.0211 (4)0.0195 (4)0.0063 (3)−0.0028 (3)−0.0042 (3)
C13A0.0254 (5)0.0475 (7)0.0212 (5)0.0185 (5)−0.0010 (4)−0.0047 (4)
C4B0.0146 (4)0.0234 (4)0.0213 (4)0.0075 (3)−0.0025 (3)−0.0052 (3)
C13B0.0254 (5)0.0475 (7)0.0212 (5)0.0185 (5)−0.0010 (4)−0.0047 (4)
C2B0.0206 (5)0.0381 (6)0.0213 (4)0.0140 (4)−0.0068 (3)−0.0085 (4)
C3B0.0151 (5)0.0232 (5)0.0196 (5)0.0072 (4)−0.0028 (4)−0.0034 (4)
O1—C11.2377 (13)C8—C8A1.4043 (14)
N9—C8A1.3686 (13)C2A—H2A0.9900
N9—C9A1.3864 (12)C2A—H2B0.9900
N9—H90.960 (17)C2B—H2C0.9900
C1—C2A1.5146 (14)C2B—H2D0.9900
C1—C2B1.5146 (14)C3A—H3A1.0000
C1—C9A1.4446 (13)C3B—H3B1.0000
C2A—C3A1.5276 (16)C4A—H4A0.9900
C2B—C3B1.439 (9)C4A—H4B0.9900
C3A—C4A1.5306 (15)C4B—H4C0.9900
C3A—C13A1.5385 (16)C4B—H4D0.9900
C3B—C13B1.616 (9)C5—H50.9500
C3B—C4B1.521 (9)C6—H60.9500
C4A—C4C1.4957 (13)C7—H70.9500
C4B—C4C1.4957 (13)C8—H80.9500
C4C—C4D1.4306 (13)C13A—H13B0.9800
C4C—C9A1.3859 (14)C13A—H13C0.9800
C4D—C51.4075 (15)C13A—H13A0.9800
C4D—C8A1.4264 (14)C13B—H13D0.9800
C5—C61.3785 (15)C13B—H13E0.9800
C6—C71.4140 (16)C13B—H13F0.9800
C7—C81.3784 (16)
O1···N92.9322 (11)H3A···O1iv2.6400
O1···C3Ai3.3896 (14)H3A···C9A3.0300
O1···C4Ai3.3747 (13)H3A···C8iii2.8700
O1···C4Bi3.3747 (13)H3A···H8iii2.3900
O1···N9ii2.8481 (12)H3B···C7v2.6200
O1···H4Ai2.7800H3B···C13A2.1300
O1···H3Ai2.6400H3B···C2A1.9700
O1···H4Ci2.4500H3B···C4A2.0500
O1···H92.813 (15)H3B···C5v2.8900
O1···H9ii1.939 (16)H3B···C6v2.4800
N9···O12.9322 (11)H4A···C1iv2.9100
N9···O1ii2.8481 (12)H4A···O1iv2.7800
C1···C8Aiii3.5679 (14)H4A···H5viii2.5500
C1···C8iii3.5708 (15)H4B···C4Dv2.9600
C2B···C13A2.5175 (17)H4B···H13C2.4900
C2B···C4A2.5384 (15)H4B···C8Av2.9900
C3A···O1iv3.3896 (14)H4C···O1iv2.4500
C3B···C6v3.458 (9)H4C···C1iv2.7900
C3B···C7v3.592 (9)H4C···C2A3.0000
C4A···O1iv3.3747 (13)H4C···C13A2.4900
C4B···C2A2.5384 (15)H4C···H13E2.3300
C4B···O1iv3.3747 (13)H4D···H5viii2.3800
C4B···C13A2.5282 (15)H4D···C8Av3.1000
C6···C3Bv3.458 (9)H4D···C13A2.9100
C7···C3Bv3.592 (9)H5···H4Dviii2.3800
C8···C1iii3.5708 (15)H5···H4Aviii2.5500
C8A···C1iii3.5679 (14)H5···H5viii2.5700
C13B···C2A2.5175 (17)H6···H13Fviii2.4600
C13B···C4A2.5282 (15)H7···H7ix2.5800
C1···H4Ci2.7900H8···H13Dx2.5100
C1···H9ii3.012 (16)H8···C13Ax2.8400
C1···H4Ai2.9100H8···H13Ax2.4900
C4D···H4Bv2.9600H8···H13Bx2.5800
C5···H3Bv2.8900H8···C13Bx2.8400
C6···H2Av3.0200H8···H3Aiii2.3900
C6···H3Bv2.4800H9···O1ii1.939 (16)
C7···H3Bv2.6200H9···O12.813 (15)
C8···H2Ciii2.9900H9···C1ii3.012 (16)
C8···H3Aiii2.8700H13A···H8vi2.4900
C8A···H4Bv2.9900H13A···H2B2.5000
C8A···H4Dv3.1000H13B···H8vi2.5800
C9A···H3A3.0300H13C···H4B2.4900
C13A···H8vi2.8400H13C···H2A2.5100
C13B···H8vi2.8400H13D···H8vi2.5100
H2A···H13C2.5100H13D···C2A2.6600
H2A···C6v3.0200H13D···H2C2.4900
H2B···H2Bvii2.4400H13E···C2A2.8000
H2B···H13A2.5000H13E···C4A2.7100
H2C···C13A2.4400H13E···H2C2.4300
H2C···H13D2.4900H13E···H4C2.3300
H2C···C8iii2.9900H13E···H13Exi2.4800
H2C···H13E2.4300H13F···C4A2.7100
H2C···C4A2.9900H13F···H6viii2.4600
H2D···C13A2.8800
C8A—N9—C9A107.71 (8)C1—C2B—H2C107.00
C9A—N9—H9126.1 (9)C1—C2B—H2D107.00
C8A—N9—H9125.8 (9)C3B—C2B—H2C107.00
O1—C1—C9A123.78 (9)C3B—C2B—H2D107.00
O1—C1—C2A121.93 (9)H2C—C2B—H2D107.00
C2B—C1—C9A114.27 (9)C4A—C3A—H3A108.00
C2A—C1—C9A114.27 (9)C13A—C3A—H3A108.00
O1—C1—C2B121.93 (9)C2A—C3A—H3A108.00
C1—C2A—C3A114.98 (9)C2B—C3B—H3B107.00
C1—C2B—C3B121.6 (3)C4B—C3B—H3B107.00
C2A—C3A—C13A110.39 (9)C13B—C3B—H3B107.00
C2A—C3A—C4A112.21 (9)C3A—C4A—H4A110.00
C4A—C3A—C13A110.93 (9)C4C—C4A—H4A110.00
C4B—C3B—C13B107.3 (5)C4C—C4A—H4B110.00
C2B—C3B—C4B118.1 (6)C3A—C4A—H4B110.00
C2B—C3B—C13B110.9 (5)H4A—C4A—H4B108.00
C3A—C4A—C4C110.43 (8)C4C—C4B—H4D109.00
C3B—C4B—C4C113.5 (3)C3B—C4B—H4C109.00
C4A—C4C—C4D131.07 (9)C3B—C4B—H4D109.00
C4A—C4C—C9A122.53 (8)H4C—C4B—H4D108.00
C4D—C4C—C9A106.40 (8)C4C—C4B—H4C109.00
C4B—C4C—C4D131.07 (9)C4D—C5—H5121.00
C4B—C4C—C9A122.53 (8)C6—C5—H5121.00
C4C—C4D—C5134.36 (9)C7—C6—H6119.00
C4C—C4D—C8A106.39 (8)C5—C6—H6119.00
C5—C4D—C8A119.23 (9)C8—C7—H7119.00
C4D—C5—C6118.82 (10)C6—C7—H7119.00
C5—C6—C7121.15 (10)C8A—C8—H8121.00
C6—C7—C8121.64 (10)C7—C8—H8121.00
C7—C8—C8A117.49 (10)H13B—C13A—H13C109.00
N9—C8A—C4D109.02 (8)H13A—C13A—H13C109.00
N9—C8A—C8129.38 (9)C3A—C13A—H13A109.00
C4D—C8A—C8121.61 (9)C3A—C13A—H13B109.00
N9—C9A—C1125.11 (9)C3A—C13A—H13C109.00
N9—C9A—C4C110.47 (8)H13A—C13A—H13B109.00
C1—C9A—C4C124.40 (9)C3B—C13B—H13D109.00
C1—C2A—H2A109.00C3B—C13B—H13E109.00
C1—C2A—H2B109.00C3B—C13B—H13F109.00
C3A—C2A—H2A109.00H13D—C13B—H13E109.00
C3A—C2A—H2B109.00H13D—C13B—H13F109.00
H2A—C2A—H2B108.00H13E—C13B—H13F109.00
C9A—N9—C8A—C4D0.74 (11)C9A—C4C—C4D—C5−176.89 (11)
C9A—N9—C8A—C8−179.21 (10)C9A—C4C—C4D—C8A1.25 (11)
C8A—N9—C9A—C1−178.64 (9)C4A—C4C—C9A—N9178.40 (9)
C8A—N9—C9A—C4C0.06 (12)C4A—C4C—C9A—C1−2.88 (15)
O1—C1—C2A—C3A152.13 (10)C4D—C4C—C9A—N9−0.84 (11)
C9A—C1—C2A—C3A−29.84 (13)C4D—C4C—C9A—C1177.89 (9)
O1—C1—C9A—N91.63 (16)C4C—C4D—C5—C6178.95 (11)
O1—C1—C9A—C4C−176.91 (10)C8A—C4D—C5—C61.00 (15)
C2A—C1—C9A—N9−176.36 (9)C4C—C4D—C8A—N9−1.24 (11)
C2A—C1—C9A—C4C5.10 (14)C4C—C4D—C8A—C8178.71 (9)
C1—C2A—C3A—C4A52.21 (13)C5—C4D—C8A—N9177.23 (9)
C1—C2A—C3A—C13A176.50 (10)C5—C4D—C8A—C8−2.82 (15)
C2A—C3A—C4A—C4C−47.27 (12)C4D—C5—C6—C71.00 (16)
C13A—C3A—C4A—C4C−171.26 (9)C5—C6—C7—C8−1.31 (17)
C3A—C4A—C4C—C4D−156.71 (10)C6—C7—C8—C8A−0.46 (16)
C3A—C4A—C4C—C9A24.26 (13)C7—C8—C8A—N9−177.55 (10)
C4A—C4C—C4D—C53.97 (19)C7—C8—C8A—C4D2.50 (15)
C4A—C4C—C4D—C8A−177.90 (10)
D—H···AD—HH···AD···AD—H···A
N9—H9···O1ii0.960 (17)1.939 (16)2.848 (1)157.2 (13)
C4A—H4B···Cg1v0.992.833.779 (1)162
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
N9—H9⋯O1i0.960 (17)1.939 (16)2.848 (1)157.2 (13)
C4A—H4B⋯Cg1ii0.992.833.779 (1)162

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the C4D,C5–C8,C8A ring.

  6 in total

Review 1.  Isolation and synthesis of biologically active carbazole alkaloids.

Authors:  Hans-Joachim Knölker; Kethiri R Reddy
Journal:  Chem Rev       Date:  2002-11       Impact factor: 60.622

2.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

3.  3-Aminotetrahydrocarbazoles as a new series of central nervous system agents.

Authors:  A Mooradian; P E Dupont; A G Hlavec; M D Aceto; J Pearl
Journal:  J Med Chem       Date:  1977-04       Impact factor: 7.446

4.  6-Meth-oxy-2,3,4,9-tetra-hydro-1H-carbazol-1-one.

Authors:  M Sridharan; K J Rajendra Prasad; A Thomas Gunaseelan; A Thiruvalluvar; A Linden
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2008-03-29

5.  1,2,3,4-tetrahydrocarbazoles as 5-HT6 serotonin receptor ligands.

Authors:  Jean Chang-Fong; Jagadeesh B Rangisetty; Małgorzata Dukat; Vincent Setola; Thomas Raffay; Bryan Roth; Richard A Glennon
Journal:  Bioorg Med Chem Lett       Date:  2004-04-19       Impact factor: 2.823

6.  Structure validation in chemical crystallography.

Authors:  Anthony L Spek
Journal:  Acta Crystallogr D Biol Crystallogr       Date:  2009-01-20
  6 in total
  3 in total

1.  2-(2,3,4,9-Tetra-hydro-1H-carbazol-1-ylidene)propane-dinitrile.

Authors:  R Archana; K Prabakaran; K J Rajendra Prasad; A Thiruvalluvar; R J Butcher
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2010-06-18

2.  8-Methyl-2,3,4,9-tetra-hydro-1H-carbazol-1-one.

Authors:  R Archana; E Yamuna; K J Rajendra Prasad; A Thiruvalluvar; R J Butcher
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2010-08-11

3.  6-Methyl-2,3,4,9-tetra-hydro-1H-carbazole-1-thione.

Authors:  R Archana; K Prabakaran; K J Rajendra Prasad; A Thiruvalluvar; R J Butcher
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2011-06-11
  3 in total

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