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Acta Cryst. (2009). E65, o698    [ doi:10.1107/S1600536809007429 ]

4-Methyl-7,8,9,10-tetrahydrocyclohepta[b]indol-6(5H)-one

M. Sridharan, K. J. Rajendra Prasad, A. Thomas Gunaseelan, A. Thiruvalluvar and R. J. Butcher

Abstract top

In the title compound, C14H15NO, the seven-membered ring exhibits a slightly distorted twist-boat conformation. The pyrrole ring forms a dihedral angle of 1.44 (10)° with the fused benzene ring. N-H...O hydrogen bonds form a centrosymmetric dimer and weak C-H...[pi] interactions are also found in the crystal structure.

Comment top

The title compound has been analysed as part of our crystallographic studies on cyclohept[b]indoles and their substituted analogues. Sridharan et al.(2008) have reported the X-ray crystal sructure of the related compound, 7,8,9,10-tetrahydro-2-methylcyclohepta[b]indol-6(5H)-one. In that paper, the seven-membered ring is stated to exhibit a slightly distorted envelope conformation.

In the title compound, C14H15NO (Fig. 1), the seven-membered ring exhibits a slightly distorted twist-boat conformation. The pyrrole ring forms a dihedral angle of 1.44 (10)° with the fused benzene ring.

N5—H5···O6(-x, -y, -z) hydrogen bonds form a centrosymmetric dimer. Furthermore, C10—H10A···π(1- x, -y, -z) and C14—H14C···π(1/2-x, -1/2+y, 1/2-z) interactions involving the pyrrole ring are present. Additionally, a C8—H8A···π(1-x, -y, -z) interaction involving the benzene ring are also found in the crystal structure.

Related literature top

For a related crystal structure, see: Sridharan et al. (2008). Cg1 is the centroid of the pyrrole ring and Cg2 is the centroid of the benzene ring.

Experimental top

A solution of 2-(2-(1-methylphenyl)hydrazono)cycloheptanone (0.230 g, 0.001 mol) in a mixture of acetic acid (20 ml) and conc. hydrochloric acid (5 ml) was refluxed on an oil bath pre-heated to 398–403 K for 4 h. The reaction was monitored by TLC. After the completion of the reaction, the contents were cooled and poured into ice water with stirring. The separated brown solid was filtered and purified by passing through a column of silica gel and eluting with a petroleum ether-ethyl acetate (95:5 v/v) mixture to yield the title compound (0.140 g, 66%). This product was recrystallized using ethanol.

Refinement top

H5 attached to N5 was located in a difference Fourier map and refined isotropically; the final N—H distance was 0.94 (3) Å. The remaining H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93, 0.96 and 0.97 Å for Csp2, methyl and methylene H atoms, respectively. Uiso(H) = xUeq(C), where x = 1.5 for methyl H atoms and 1.2 for other C-bound H atoms.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radius.
[Figure 2] Fig. 2. The 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.
4-Methyl-7,8,9,10-tetrahydrocyclohepta[b]indol-6(5H)-one top
Crystal data top
C14H15NOF(000) = 456
Mr = 213.27Dx = 1.261 Mg m−3
Monoclinic, P21/nMelting point: 412.5 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 9.6731 (4) ÅCell parameters from 3217 reflections
b = 10.0924 (5) Åθ = 4.7–32.7°
c = 11.8328 (6) ŵ = 0.08 mm−1
β = 103.397 (5)°T = 295 K
V = 1123.74 (10) Å3Prism, colourless
Z = 40.55 × 0.45 × 0.26 mm
Data collection top
Oxford Diffraction Gemini R
diffractometer		3772 independent reflections
Radiation source: fine-focus sealed tube2044 reflections with I > 2σ(I)
graphiteRint = 0.025
Detector resolution: 10.5081 pixels mm-1θmax = 32.8°, θmin = 4.7°
φ and ω scansh = −14→13
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)		k = −14→15
Tmin = 0.937, Tmax = 1.000l = −17→15
9586 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.077Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.253H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.1467P)2]
where P = (Fo2 + 2Fc2)/3
3772 reflections(Δ/σ)max = 0.001
150 parametersΔρmax = 0.57 e Å−3
0 restraintsΔρmin = −0.29 e Å−3
Crystal data top
C14H15NOV = 1123.74 (10) Å3
Mr = 213.27Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.6731 (4) ŵ = 0.08 mm−1
b = 10.0924 (5) ÅT = 295 K
c = 11.8328 (6) Å0.55 × 0.45 × 0.26 mm
β = 103.397 (5)°
Data collection top
Oxford Diffraction Gemini R
diffractometer		3772 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)		2044 reflections with I > 2σ(I)
Tmin = 0.937, Tmax = 1.000Rint = 0.025
9586 measured reflectionsθmax = 32.8°
Refinement top
R[F2 > 2σ(F2)] = 0.077H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.253Δρmax = 0.57 e Å−3
S = 1.04Δρmin = −0.29 e Å−3
3772 reflectionsAbsolute structure: ?
150 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
xyzUiso*/Ueq
O60.07595 (15)0.12098 (15)−0.05930 (13)0.0619 (5)
N50.23136 (16)−0.06788 (15)0.07124 (12)0.0407 (4)
C10.5759 (2)−0.1262 (3)0.25005 (19)0.0684 (9)
C20.5665 (3)−0.2535 (3)0.2849 (2)0.0765 (9)
C30.4432 (3)−0.3286 (3)0.24770 (18)0.0677 (9)
C40.3234 (2)−0.2780 (2)0.17452 (17)0.0523 (7)
C4A0.33242 (19)−0.14568 (19)0.14131 (14)0.0430 (5)
C5A0.28716 (17)0.05736 (17)0.06406 (14)0.0398 (5)
C60.19212 (19)0.15599 (19)−0.00273 (15)0.0445 (6)
C70.2291 (3)0.3012 (2)0.0012 (2)0.0648 (8)
C80.3799 (3)0.3459 (3)0.0216 (3)0.0855 (11)
C90.4803 (3)0.3090 (3)0.1286 (3)0.0892 (11)
C100.5353 (2)0.1680 (3)0.1405 (2)0.0624 (8)
C10A0.42772 (18)0.05965 (19)0.12696 (15)0.0453 (6)
C10B0.45656 (19)−0.0687 (2)0.17618 (15)0.0479 (6)
C140.1923 (3)−0.3579 (2)0.1263 (2)0.0715 (9)
H10.65958−0.078270.274660.0820*
H20.64462−0.291830.335040.0916*
H30.44200−0.415580.273290.0813*
H50.134 (3)−0.084 (2)0.0449 (18)0.054 (6)*
H7A0.178780.33949−0.072010.0777*
H7B0.189460.340960.061340.0777*
H8A0.417360.31357−0.042490.1026*
H8B0.379280.441910.017070.1026*
H9A0.435640.326120.192520.1070*
H9B0.561570.367660.138190.1070*
H10A0.591250.154380.083270.0749*
H10B0.599050.159030.216540.0749*
H14A0.18522−0.374730.045260.1074*
H14B0.11011−0.309590.135420.1074*
H14C0.19759−0.440580.167190.1074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O60.0446 (8)0.0549 (9)0.0752 (10)−0.0084 (6)−0.0088 (7)0.0151 (7)
N50.0350 (7)0.0400 (8)0.0453 (8)−0.0003 (6)0.0054 (6)0.0036 (6)
C10.0434 (11)0.102 (2)0.0559 (12)0.0226 (12)0.0035 (9)0.0005 (12)
C20.0640 (14)0.107 (2)0.0565 (13)0.0439 (15)0.0101 (10)0.0127 (13)
C30.0818 (17)0.0718 (15)0.0551 (12)0.0387 (13)0.0272 (12)0.0185 (11)
C40.0636 (12)0.0531 (12)0.0473 (10)0.0179 (10)0.0273 (9)0.0090 (8)
C4A0.0408 (9)0.0520 (11)0.0379 (8)0.0101 (8)0.0125 (7)0.0001 (7)
C5A0.0354 (8)0.0431 (10)0.0407 (8)−0.0049 (7)0.0083 (6)−0.0033 (7)
C60.0427 (10)0.0447 (10)0.0442 (9)−0.0046 (8)0.0062 (7)0.0041 (7)
C70.0683 (14)0.0483 (12)0.0718 (14)−0.0129 (10)0.0043 (11)0.0063 (10)
C80.0817 (19)0.0623 (16)0.113 (2)−0.0267 (14)0.0236 (16)0.0034 (15)
C90.0805 (18)0.082 (2)0.0953 (19)−0.0445 (16)0.0002 (15)−0.0061 (15)
C100.0384 (10)0.0861 (17)0.0602 (12)−0.0196 (10)0.0065 (8)−0.0131 (11)
C10A0.0356 (9)0.0608 (12)0.0390 (8)−0.0029 (8)0.0074 (7)−0.0079 (8)
C10B0.0393 (9)0.0648 (13)0.0388 (9)0.0101 (8)0.0073 (7)−0.0038 (8)
C140.095 (2)0.0499 (12)0.0785 (15)0.0098 (12)0.0380 (14)0.0109 (11)
Geometric parameters (Å, °) top
O6—C61.220 (2)C10—C10A1.492 (3)
N5—C4A1.373 (2)C10A—C10B1.421 (3)
N5—C5A1.385 (2)C1—H10.9300
N5—H50.94 (3)C2—H20.9300
C1—C10B1.402 (3)C3—H30.9300
C1—C21.359 (4)C7—H7A0.9700
C2—C31.396 (4)C7—H7B0.9700
C3—C41.374 (3)C8—H8A0.9700
C4—C4A1.401 (3)C8—H8B0.9700
C4—C141.500 (3)C9—H9A0.9700
C4A—C10B1.409 (3)C9—H9B0.9700
C5A—C61.457 (3)C10—H10A0.9700
C5A—C10A1.391 (2)C10—H10B0.9700
C6—C71.507 (3)C14—H14A0.9600
C7—C81.492 (4)C14—H14B0.9600
C8—C91.454 (5)C14—H14C0.9600
C9—C101.514 (4)
O6···N52.684 (2)H5···O62.41 (2)
O6···N5i2.992 (2)H5···C142.94 (2)
O6···H52.41 (2)H5···H14B2.5500
O6···H5i2.11 (3)H5···O6i2.11 (3)
O6···H14Bi2.6300H7A···H10Bvii2.4400
N5···O62.684 (2)H7B···H9A2.5300
N5···O6i2.992 (2)H7B···H14Cviii2.5300
N5···H14B2.8800H8A···H10A2.5400
N5···H10Aii2.9200H8A···C2ii2.9700
C3···C6iii3.560 (3)H8A···C3ii3.0400
C6···C3iv3.560 (3)H9A···H7B2.5300
C10A···C14iv3.484 (3)H9A···H14Biv2.5800
C14···C10Aiii3.484 (3)H10A···H8A2.5400
C1···H10B2.9200H10A···H2v2.5700
C2···H8Aii2.9700H10A···N5ii2.9200
C3···H8Aii3.0400H10A···C4Aii2.9200
C4A···H10Aii2.9200H10B···C12.9200
C10···H2v3.0700H10B···H12.5200
C10···H13.0400H10B···H7Aix2.4400
C10A···H14Civ2.9600H14B···N52.8800
C10B···H14Civ2.9300H14B···H52.5500
C14···H52.94 (2)H14B···H9Aiii2.5800
H1···C103.0400H14B···O6i2.6300
H1···H10B2.5200H14C···H32.4200
H2···C10vi3.0700H14C···H7Bx2.5300
H2···H10Avi2.5700H14C···C10Aiii2.9600
H3···H14C2.4200H14C···C10Biii2.9300
C4A—N5—C5A109.03 (15)C1—C2—H2119.00
C4A—N5—H5128.5 (13)C3—C2—H2119.00
C5A—N5—H5121.0 (13)C2—C3—H3119.00
C2—C1—C10B118.5 (2)C4—C3—H3119.00
C1—C2—C3122.0 (2)C6—C7—H7A107.00
C2—C3—C4122.1 (3)C6—C7—H7B107.00
C4A—C4—C14120.54 (18)C8—C7—H7A107.00
C3—C4—C4A115.7 (2)C8—C7—H7B107.00
C3—C4—C14123.7 (2)H7A—C7—H7B107.00
N5—C4A—C4129.27 (17)C7—C8—H8A107.00
N5—C4A—C10B107.50 (16)C7—C8—H8B107.00
C4—C4A—C10B123.21 (17)C9—C8—H8A107.00
N5—C5A—C6116.80 (15)C9—C8—H8B107.00
C6—C5A—C10A133.99 (17)H8A—C8—H8B107.00
N5—C5A—C10A109.21 (15)C8—C9—H9A108.00
O6—C6—C7118.74 (19)C8—C9—H9B108.00
C5A—C6—C7122.15 (17)C10—C9—H9A108.00
O6—C6—C5A119.02 (17)C10—C9—H9B108.00
C6—C7—C8121.0 (2)H9A—C9—H9B107.00
C7—C8—C9119.6 (3)C9—C10—H10A108.00
C8—C9—C10118.1 (3)C9—C10—H10B108.00
C9—C10—C10A117.22 (19)C10A—C10—H10A108.00
C5A—C10A—C10B106.20 (16)C10A—C10—H10B108.00
C10—C10A—C10B123.93 (17)H10A—C10—H10B107.00
C5A—C10A—C10129.83 (18)C4—C14—H14A109.00
C4A—C10B—C10A108.03 (16)C4—C14—H14B109.00
C1—C10B—C4A118.49 (19)C4—C14—H14C110.00
C1—C10B—C10A133.5 (2)H14A—C14—H14B109.00
C2—C1—H1121.00H14A—C14—H14C109.00
C10B—C1—H1121.00H14B—C14—H14C109.00
C5A—N5—C4A—C4179.17 (18)N5—C5A—C6—C7167.99 (18)
C5A—N5—C4A—C10B−1.88 (19)C10A—C5A—C6—O6172.63 (19)
C4A—N5—C5A—C6−177.17 (15)C10A—C5A—C6—C7−11.0 (3)
C4A—N5—C5A—C10A2.05 (19)N5—C5A—C10A—C10176.20 (19)
C10B—C1—C2—C31.2 (4)N5—C5A—C10A—C10B−1.36 (19)
C2—C1—C10B—C4A−0.1 (3)C6—C5A—C10A—C10−4.8 (3)
C2—C1—C10B—C10A177.7 (2)C6—C5A—C10A—C10B177.67 (18)
C1—C2—C3—C4−0.7 (4)O6—C6—C7—C8−153.2 (2)
C2—C3—C4—C4A−1.0 (3)C5A—C6—C7—C830.4 (3)
C2—C3—C4—C14175.8 (2)C6—C7—C8—C9−60.2 (4)
C3—C4—C4A—N5−179.06 (19)C7—C8—C9—C1075.5 (4)
C3—C4—C4A—C10B2.1 (3)C8—C9—C10—C10A−56.8 (3)
C14—C4—C4A—N54.0 (3)C9—C10—C10A—C5A27.5 (3)
C14—C4—C4A—C10B−174.77 (19)C9—C10—C10A—C10B−155.4 (2)
N5—C4A—C10B—C1179.35 (17)C5A—C10A—C10B—C1−177.8 (2)
N5—C4A—C10B—C10A1.0 (2)C5A—C10A—C10B—C4A0.2 (2)
C4—C4A—C10B—C1−1.6 (3)C10—C10A—C10B—C14.5 (3)
C4—C4A—C10B—C10A−179.94 (17)C10—C10A—C10B—C4A−177.54 (18)
N5—C5A—C6—O6−8.4 (2)
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+3/2, y+1/2, −z+1/2; (vi) −x+3/2, y−1/2, −z+1/2; (vii) x−1/2, −y+1/2, z−1/2; (viii) x, y+1, z; (ix) x+1/2, −y+1/2, z+1/2; (x) x, y−1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H5···O6i0.94 (3)2.11 (3)2.992 (2)156.6 (19)
C10—H10A···Cg1ii0.972.843.736 (2)154
C14—H14C···Cg1iii0.962.863.621 (2)137
C8—H8A···Cg2ii0.972.873.830 (3)173
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z; (iii) −x+1/2, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H5···O6i0.94 (3)2.11 (3)2.992 (2)156.6 (19)
C10—H10A···Cg1ii0.972.843.736 (2)154
C14—H14C···Cg1iii0.962.863.621 (2)137
C8—H8A···Cg2ii0.972.873.830 (3)173
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z; (iii) −x+1/2, y−1/2, −z+1/2.
Acknowledgements top

We acknowledge the UGC, New Delhi, India, for the award of Major Research Project grant No. F.No.31-122/2005. MS thanks the UGC, New Delhi, India, for the award of research fellowship. AT thanks the UGC, New Delhi, 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 (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

references
References top

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Sridharan, M., Prasad, K. J. R., Ngendahimana, A. & Zeller, M. (2008). Acta Cryst. E64, o1207.