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

Archana, R.; Yamuna, E.; Rajendra Prasad, K.J.; Thiruvalluvar, A.; Butcher, R.J.

doi:10.1107/S1600536811016229

organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Page o1325

doi:10.1107/S1600536811016229

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

R. Archana,^a E. Yamuna,^b K. J. Rajendra Prasad,^b A. Thiruvalluvar ^a ^* and R. J. Butcher ^c

^aPG Research Department of Physics, Rajah Serfoji Government College (Autonomous), Thanjavur 613 005, Tamilnadu, India, ^bDepartment of Chemistry, Bharathiar University, Coimbatore 641 046, Tamilnadu, India, and ^cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: thiruvalluvar.a@gmail.com

(Received 26 April 2011; accepted 28 April 2011; online 7 May 2011)

In the title molecule, C₁₄H₁₅NO, the dihedral angle between the benzene and pyrrole rings is 1.99 (12)°. The cycloheptene ring adopts a slightly distorted boat conformation.

Related literature

For the interest and importance of indole derivatives, see: Csomós et al. (2007 ). For pyrido-fused cyclohept[b]indole alkaloids, see: Bennasar et al. (1997 ). For crystallographic studies of cyclohept[b]indoles, see: Archana et al. (2010 ).

Experimental

Crystal data

C₁₄H₁₅NO
M_r = 213.27
Orthorhombic, P c a 2₁
a = 8.6999 (2) Å
b = 14.1805 (3) Å
c = 9.1392 (3) Å
V = 1127.49 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.62 mm⁻¹
T = 295 K
0.47 × 0.35 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.803, T_max = 1.000
1184 measured reflections
1184 independent reflections
1148 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.106
S = 1.07
1184 reflections
147 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811016229/hg5032sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016229/hg5032Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811016229/hg5032Isup3.cml

checkCIF report

Comment top

Indole derivatives condensed with different heterocycles are physiologically active compounds found in abundance in materials such as pharmaceuticals, alkaloids and potential therapeutic agents (Csomós et al., 2007). Ervitsine and Ervatamine (Bennasar et al., 1997) were important class of pyrido fused cyclohept[b]indole alkaloids. Recently we have reported crystallographic studies for some cyclohept[b]indoles in our laboratory (Archana et al., 2010).

The molecular structure of the title compound, with atomic numbering scheme, is shown in Fig. 1. In the title molecule, C₁₄H₁₅NO, the dihedral angle between the benzene and pyrrole rings is 1.99 (12)°. The cycloheptene ring adopts a slightly distorted boat conformation.

Related literature top

For the interest and importance of indole derivatives, see: Csomós et al. (2007). For pyrido-fused cyclohept[b]indole alkaloids, see: Bennasar et al. (1997). For crystallographic studies of cyclohept[b]indoles, see: Archana et al. (2010).

Experimental top

To a solution of 7,8,9,10-tetrahydrocyclohepta[b]indol-6(5H)-one (0.199 g, 0.001 mol) in 5 ml acetone added powdered KOH (0.280 g, 0.005 mol) in ice cold condition. After few minutes methyl iodide (0.13 ml, 0.002 mol) was added drop by drop with vigorous stirring and the reaction mixture was stirrired for 15 min at room temperature. Benzene was added to the reaction mixture and insoluble materials are removed by filtration. The benzene solution was washed with saturated NaCl solution, dried by using Na₂SO₄ and evaporation yielded the title compound (0.191 g, 90%). This was recrystallized from benzene and ethyl acetate mixture.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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

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.

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

Crystal data top

C₁₄H₁₅NO	D_x = 1.256 Mg m⁻³
M_r = 213.27	Melting point: 338 K
Orthorhombic, Pca2₁	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2c -2ac	Cell parameters from 2006 reflections
a = 8.6999 (2) Å	θ = 4.8–73.4°
b = 14.1805 (3) Å	µ = 0.62 mm⁻¹
c = 9.1392 (3) Å	T = 295 K
V = 1127.49 (5) Å³	Chunk, pale-yellow
Z = 4	0.47 × 0.35 × 0.20 mm
F(000) = 456

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	1184 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1148 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 10.5081 pixels mm^-1	θ_max = 73.6°, θ_min = 6.0°
ω scans	h = 0→10
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = 0→17
T_min = 0.803, T_max = 1.000	l = 0→11
1184 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.037	w = 1/[σ²(F_o²) + (0.0678P)² + 0.0651P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.106	(Δ/σ)_max = 0.001
S = 1.07	Δρ_max = 0.14 e Å⁻³
1184 reflections	Δρ_min = −0.13 e Å⁻³
147 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.018 (2)
Primary atom site location: structure-invariant direct methods	Absolute structure: see Refinement section in Supplementary materials
Secondary atom site location: difference Fourier map

Crystal data top

C₁₄H₁₅NO	V = 1127.49 (5) Å³
M_r = 213.27	Z = 4
Orthorhombic, Pca2₁	Cu Kα radiation
a = 8.6999 (2) Å	µ = 0.62 mm⁻¹
b = 14.1805 (3) Å	T = 295 K
c = 9.1392 (3) Å	0.47 × 0.35 × 0.20 mm

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	1184 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	1148 reflections with I > 2σ(I)
T_min = 0.803, T_max = 1.000	R_int = 0.020
1184 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	1 restraint
wR(F²) = 0.106	H-atom parameters constrained
S = 1.07	Δρ_max = 0.14 e Å⁻³
1184 reflections	Δρ_min = −0.13 e Å⁻³
147 parameters	Absolute structure: see Refinement section in Supplementary materials

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

	x	y	z	U_iso*/U_eq
O6	0.5677 (3)	0.05292 (17)	0.4636 (4)	0.1141 (10)
N5	0.4250 (2)	0.18603 (13)	0.6610 (2)	0.0514 (5)
C1	0.4932 (3)	0.42768 (16)	0.7515 (3)	0.0607 (8)
C2	0.3719 (3)	0.4495 (2)	0.8403 (4)	0.0792 (10)
C3	0.2600 (4)	0.3822 (2)	0.8755 (4)	0.0826 (10)
C4	0.2661 (3)	0.2923 (2)	0.8220 (3)	0.0686 (9)
C4A	0.3895 (2)	0.26879 (16)	0.7301 (2)	0.0512 (7)
C5	0.3392 (3)	0.09825 (18)	0.6805 (4)	0.0791 (10)
C5A	0.5637 (3)	0.19791 (14)	0.5882 (2)	0.0471 (6)
C6	0.6360 (4)	0.12408 (16)	0.4995 (3)	0.0637 (9)
C7	0.7989 (3)	0.13870 (18)	0.4529 (3)	0.0669 (9)
C8	0.9072 (3)	0.1731 (2)	0.5724 (3)	0.0713 (9)
C9	0.9058 (3)	0.2786 (2)	0.6046 (3)	0.0647 (8)
C10	0.7621 (3)	0.33087 (14)	0.5528 (3)	0.0533 (6)
C10A	0.6154 (2)	0.28910 (14)	0.6081 (2)	0.0431 (5)
C10B	0.5048 (2)	0.33542 (14)	0.6960 (2)	0.0458 (6)
H1	0.56661	0.47293	0.72821	0.0728*
H2	0.36341	0.51021	0.87808	0.0950*
H3	0.17945	0.39907	0.93704	0.0989*
H4	0.19098	0.24819	0.84567	0.0823*
H5A	0.25845	0.10790	0.75052	0.1184*
H5B	0.29541	0.07936	0.58858	0.1184*
H5C	0.40722	0.04986	0.71507	0.1184*
H7A	0.83814	0.07958	0.41476	0.0803*
H7B	0.80020	0.18409	0.37351	0.0803*
H8A	0.88223	0.13988	0.66208	0.0856*
H8B	1.01113	0.15535	0.54543	0.0856*
H9A	0.91596	0.28753	0.70940	0.0776*
H9B	0.99487	0.30708	0.55857	0.0776*
H10A	0.76018	0.33072	0.44669	0.0640*
H10B	0.76828	0.39599	0.58476	0.0640*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O6	0.131 (2)	0.0782 (13)	0.133 (2)	−0.0248 (14)	0.030 (2)	−0.0505 (16)
N5	0.0472 (9)	0.0535 (9)	0.0534 (10)	−0.0053 (7)	−0.0045 (8)	0.0057 (8)
C1	0.0620 (13)	0.0556 (12)	0.0644 (14)	0.0153 (10)	−0.0049 (12)	−0.0035 (11)
C2	0.0837 (19)	0.0764 (16)	0.0774 (18)	0.0354 (15)	0.0030 (16)	−0.0123 (16)
C3	0.0671 (15)	0.111 (2)	0.0696 (17)	0.0405 (18)	0.0133 (15)	0.0049 (17)
C4	0.0442 (12)	0.0964 (17)	0.0652 (15)	0.0115 (12)	0.0043 (11)	0.0162 (15)
C4A	0.0408 (10)	0.0643 (12)	0.0486 (12)	0.0048 (9)	−0.0069 (9)	0.0089 (10)
C5	0.0732 (17)	0.0691 (14)	0.095 (2)	−0.0234 (13)	−0.0062 (17)	0.0152 (16)
C5A	0.0508 (11)	0.0484 (10)	0.0421 (10)	0.0017 (8)	−0.0035 (9)	0.0048 (9)
C6	0.0855 (18)	0.0514 (12)	0.0541 (14)	0.0054 (11)	−0.0011 (13)	−0.0046 (10)
C7	0.0838 (18)	0.0654 (13)	0.0514 (13)	0.0252 (12)	0.0133 (13)	0.0021 (11)
C8	0.0639 (14)	0.0833 (17)	0.0668 (16)	0.0278 (13)	0.0048 (13)	0.0131 (15)
C9	0.0421 (11)	0.0857 (16)	0.0663 (15)	0.0022 (11)	0.0033 (11)	0.0069 (14)
C10	0.0538 (11)	0.0519 (9)	0.0542 (13)	−0.0005 (9)	0.0045 (10)	0.0087 (9)
C10A	0.0436 (10)	0.0438 (8)	0.0418 (10)	0.0050 (7)	−0.0036 (8)	0.0043 (8)
C10B	0.0421 (10)	0.0506 (10)	0.0448 (11)	0.0083 (7)	−0.0055 (8)	0.0029 (8)

Geometric parameters (Å, º) top

O6—C6	1.216 (4)	C10A—C10B	1.415 (3)
N5—C4A	1.368 (3)	C1—H1	0.9300
N5—C5	1.462 (3)	C2—H2	0.9300
N5—C5A	1.388 (3)	C3—H3	0.9300
C1—C2	1.367 (4)	C4—H4	0.9300
C1—C10B	1.407 (3)	C5—H5A	0.9600
C2—C3	1.401 (4)	C5—H5B	0.9600
C3—C4	1.366 (4)	C5—H5C	0.9600
C4—C4A	1.403 (3)	C7—H7A	0.9700
C4A—C10B	1.413 (3)	C7—H7B	0.9700
C5A—C6	1.466 (3)	C8—H8A	0.9700
C5A—C10A	1.381 (3)	C8—H8B	0.9700
C6—C7	1.494 (4)	C9—H9A	0.9700
C7—C8	1.523 (4)	C9—H9B	0.9700
C8—C9	1.525 (4)	C10—H10A	0.9700
C9—C10	1.529 (4)	C10—H10B	0.9700
C10—C10A	1.495 (3)

C4A—N5—C5	123.97 (19)	C2—C3—H3	119.00
C4A—N5—C5A	108.26 (17)	C4—C3—H3	119.00
C5—N5—C5A	127.26 (19)	C3—C4—H4	121.00
C2—C1—C10B	118.7 (2)	C4A—C4—H4	121.00
C1—C2—C3	121.3 (3)	N5—C5—H5A	109.00
C2—C3—C4	121.8 (3)	N5—C5—H5B	109.00
C3—C4—C4A	117.8 (3)	N5—C5—H5C	110.00
N5—C4A—C4	130.8 (2)	H5A—C5—H5B	109.00
N5—C4A—C10B	108.16 (16)	H5A—C5—H5C	109.00
C4—C4A—C10B	121.1 (2)	H5B—C5—H5C	109.00
N5—C5A—C6	123.5 (2)	C6—C7—H7A	108.00
N5—C5A—C10A	109.49 (18)	C6—C7—H7B	108.00
C6—C5A—C10A	127.0 (2)	C8—C7—H7A	108.00
O6—C6—C5A	122.2 (3)	C8—C7—H7B	108.00
O6—C6—C7	120.1 (3)	H7A—C7—H7B	107.00
C5A—C6—C7	117.7 (2)	C7—C8—H8A	108.00
C6—C7—C8	115.3 (2)	C7—C8—H8B	108.00
C7—C8—C9	116.6 (2)	C9—C8—H8A	108.00
C8—C9—C10	115.0 (2)	C9—C8—H8B	108.00
C9—C10—C10A	113.67 (19)	H8A—C8—H8B	107.00
C5A—C10A—C10	127.19 (19)	C8—C9—H9A	109.00
C5A—C10A—C10B	106.73 (17)	C8—C9—H9B	109.00
C10—C10A—C10B	126.05 (18)	C10—C9—H9A	108.00
C1—C10B—C4A	119.44 (18)	C10—C9—H9B	108.00
C1—C10B—C10A	133.24 (19)	H9A—C9—H9B	108.00
C4A—C10B—C10A	107.31 (17)	C9—C10—H10A	109.00
C2—C1—H1	121.00	C9—C10—H10B	109.00
C10B—C1—H1	121.00	C10A—C10—H10A	109.00
C1—C2—H2	119.00	C10A—C10—H10B	109.00
C3—C2—H2	119.00	H10A—C10—H10B	108.00

C5—N5—C4A—C4	−4.8 (4)	N5—C5A—C6—O6	12.5 (4)
C5—N5—C4A—C10B	174.5 (2)	N5—C5A—C6—C7	−167.6 (2)
C5A—N5—C4A—C4	−177.2 (2)	C10A—C5A—C6—O6	−164.4 (3)
C5A—N5—C4A—C10B	2.2 (2)	C10A—C5A—C6—C7	15.4 (4)
C4A—N5—C5A—C6	−178.7 (2)	N5—C5A—C10A—C10	177.9 (2)
C4A—N5—C5A—C10A	−1.3 (2)	N5—C5A—C10A—C10B	−0.1 (2)
C5—N5—C5A—C6	9.3 (4)	C6—C5A—C10A—C10	−4.8 (4)
C5—N5—C5A—C10A	−173.3 (2)	C6—C5A—C10A—C10B	177.2 (2)
C10B—C1—C2—C3	−0.4 (5)	O6—C6—C7—C8	−134.4 (3)
C2—C1—C10B—C4A	1.6 (3)	C5A—C6—C7—C8	45.7 (3)
C2—C1—C10B—C10A	−177.2 (2)	C6—C7—C8—C9	−81.6 (3)
C1—C2—C3—C4	−0.6 (5)	C7—C8—C9—C10	19.9 (3)
C2—C3—C4—C4A	0.3 (5)	C8—C9—C10—C10A	54.1 (3)
C3—C4—C4A—N5	−179.7 (3)	C9—C10—C10A—C5A	−57.7 (3)
C3—C4—C4A—C10B	1.0 (4)	C9—C10—C10A—C10B	119.9 (2)
N5—C4A—C10B—C1	178.60 (19)	C5A—C10A—C10B—C1	−179.6 (2)
N5—C4A—C10B—C10A	−2.3 (2)	C5A—C10A—C10B—C4A	1.5 (2)
C4—C4A—C10B—C1	−2.0 (3)	C10—C10A—C10B—C1	2.4 (4)
C4—C4A—C10B—C10A	177.16 (19)	C10—C10A—C10B—C4A	−176.58 (19)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₅NO
M_r	213.27
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	295
a, b, c (Å)	8.6999 (2), 14.1805 (3), 9.1392 (3)
V (Å³)	1127.49 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.62
Crystal size (mm)	0.47 × 0.35 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)
T_min, T_max	0.803, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	1184, 1184, 1148
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.622

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.106, 1.07
No. of reflections	1184
No. of parameters	147
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.13
Absolute structure	See Refinement section in Supplementary materials

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009).

Acknowledgements

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

References

Archana, R., Yamuna, E., Rajendra Prasad, K. J., Thiruvalluvar, A. & Butcher, R. J. (2010). Acta Cryst. E66, o2882. Web of Science CSD CrossRef IUCr Journals Google Scholar
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