1-Meth­oxy-2-methyl-1H-benzo[f]indole-3-carbonitrile

Li, J.-S.; He, Q.-X.; Li, P.-Y.

doi:10.1107/S1600536809052416

organic compounds

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Volume 66| Part 1| January 2010| Page o97

doi:10.1107/S1600536809052416

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1-Methoxy-2-methyl-1H-benzo[f]indole-3-carbonitrile

Jiang-Sheng Li,^a ^* Qi-Xi He ^b and Peng-Yu Li ^a

^aSchool of Chemistry and Biological Engineering, Changsha University of Science & Technology, Changsha 410004, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, People's Republic of China
^*Correspondence e-mail: js_li@yahoo.com.cn

(Received 5 December 2009; accepted 6 December 2009; online 9 December 2009)

Apart from the methyl group of the methoxy fragment, the title compound, C₁₅H₁₂N₂O, is almost planar (r.m.s. deviation = 0.045 Å); the C atom deviates from the mean plane by 1.216 (1) Å. In the crystal, π–π stacking [shortest centroid–centroid separation = 3.4652 (10) Å] and C—H⋯π interactions occur.

Related literature

For the synthesis, see: Du et al. (2008 ).

Experimental

Crystal data

C₁₅H₁₂N₂O
M_r = 236.27
Monoclinic, C 2/c
a = 18.663 (4) Å
b = 7.3763 (15) Å
c = 18.589 (4) Å
β = 113.46 (3)°
V = 2347.6 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.16 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.983, T_max = 0.986
11412 measured reflections
2060 independent reflections
1858 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.094
S = 1.04
2060 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C4–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cg3ⁱ	0.93	2.65	3.3956 (15)	138
Symmetry code: (i) $[x, -y-1, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052416/hb5274sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052416/hb5274Isup2.hkl

checkCIF report

Comment top

The title compound, (I), comprises of a benzo ring and its fused indole ring (Fig. 1). The aromatic skeleton is essentially planar.

In the crystal packing, π-π stacking interaction and C—H···π interaction help establish the molecular packing. The shortest centroid-centroid separation is 3.4652 (10) Å, which occurs between the pyrrole parts of the molecules.

Related literature top

For the synthesis, see: Du et al. (2008).

Experimental top

The compound was obtained according to the method of Du and his coworkers (2008). Colourless block of (I) was grown by slow evaporation of its ethanolic solution.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing displacement ellipsoids drawn at the 50% probability level.

1-Methoxy-2-methyl-1H-benzo[f]indole-3-carbonitrile top

Crystal data top

C₁₅H₁₂N₂O	F(000) = 992
M_r = 236.27	D_x = 1.337 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3553 reflections
a = 18.663 (4) Å	θ = 2.2–27.9°
b = 7.3763 (15) Å	µ = 0.09 mm⁻¹
c = 18.589 (4) Å	T = 113 K
β = 113.46 (3)°	Block, colourless
V = 2347.6 (8) Å³	0.20 × 0.18 × 0.16 mm
Z = 8

Data collection top

Rigaku Saturn CCD diffractometer	2060 independent reflections
Radiation source: rotating anode	1858 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.035
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.4°
ω and ϕ scans	h = −22→22
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −8→8
T_min = 0.983, T_max = 0.986	l = −22→22
11412 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0542P)² + 1.1054P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2060 reflections	Δρ_max = 0.19 e Å⁻³
166 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0212 (18)

Crystal data top

C₁₅H₁₂N₂O	V = 2347.6 (8) Å³
M_r = 236.27	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 18.663 (4) Å	µ = 0.09 mm⁻¹
b = 7.3763 (15) Å	T = 113 K
c = 18.589 (4) Å	0.20 × 0.18 × 0.16 mm
β = 113.46 (3)°

Data collection top

Rigaku Saturn CCD diffractometer	2060 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1858 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.986	R_int = 0.035
11412 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.04	Δρ_max = 0.19 e Å⁻³
2060 reflections	Δρ_min = −0.16 e Å⁻³
166 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 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) top

	x	y	z	U_iso*/U_eq
O1	0.43321 (5)	0.84231 (12)	0.08385 (5)	0.0257 (3)
N1	0.35813 (6)	0.90176 (14)	0.06827 (6)	0.0203 (3)
N2	0.11930 (6)	1.14000 (15)	−0.10753 (6)	0.0269 (3)
C1	0.32134 (7)	0.87498 (16)	0.11865 (7)	0.0194 (3)
C2	0.34992 (7)	0.79261 (17)	0.19296 (7)	0.0223 (3)
H2	0.4010	0.7503	0.2163	0.027*
C3	0.29960 (7)	0.77742 (16)	0.22936 (7)	0.0223 (3)
H3	0.3171	0.7248	0.2789	0.027*
C4	0.22060 (7)	0.83997 (16)	0.19371 (7)	0.0201 (3)
C5	0.16852 (7)	0.81573 (17)	0.23131 (7)	0.0235 (3)
H5	0.1861	0.7589	0.2800	0.028*
C6	0.09292 (7)	0.87424 (18)	0.19742 (7)	0.0256 (3)
H6	0.0597	0.8579	0.2232	0.031*
C7	0.06515 (8)	0.95940 (18)	0.12338 (7)	0.0249 (3)
H7	0.0138	1.0002	0.1008	0.030*
C8	0.11331 (7)	0.98234 (16)	0.08458 (7)	0.0208 (3)
H8	0.0941	1.0372	0.0355	0.025*
C9	0.19198 (7)	0.92382 (15)	0.11816 (7)	0.0181 (3)
C10	0.24518 (7)	0.93956 (15)	0.08037 (7)	0.0181 (3)
C11	0.23885 (7)	1.00368 (15)	0.00486 (7)	0.0185 (3)
C12	0.31010 (7)	0.97803 (16)	−0.00040 (7)	0.0195 (3)
C13	0.33588 (8)	1.02295 (18)	−0.06433 (7)	0.0253 (3)
H13A	0.3631	1.1367	−0.0531	0.038*
H13B	0.2911	1.0317	−0.1131	0.038*
H13C	0.3700	0.9295	−0.0681	0.038*
C14	0.48901 (8)	0.9831 (2)	0.12264 (9)	0.0327 (4)
H14A	0.4818	1.0829	0.0873	0.049*
H14B	0.5410	0.9362	0.1383	0.049*
H14C	0.4813	1.0239	0.1681	0.049*
C15	0.17262 (7)	1.07923 (16)	−0.05700 (7)	0.0196 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0194 (5)	0.0244 (5)	0.0344 (5)	0.0039 (4)	0.0119 (4)	−0.0008 (4)
N1	0.0163 (5)	0.0211 (5)	0.0235 (6)	0.0016 (4)	0.0079 (4)	−0.0004 (4)
N2	0.0258 (6)	0.0317 (7)	0.0227 (6)	0.0015 (5)	0.0093 (5)	0.0016 (5)
C1	0.0211 (6)	0.0161 (6)	0.0216 (6)	−0.0016 (5)	0.0090 (5)	−0.0021 (5)
C2	0.0203 (6)	0.0193 (6)	0.0237 (7)	0.0015 (5)	0.0049 (5)	−0.0005 (5)
C3	0.0274 (7)	0.0180 (6)	0.0190 (6)	−0.0013 (5)	0.0067 (5)	0.0008 (5)
C4	0.0241 (7)	0.0155 (6)	0.0201 (6)	−0.0031 (5)	0.0082 (5)	−0.0034 (5)
C5	0.0300 (7)	0.0205 (6)	0.0200 (6)	−0.0063 (5)	0.0100 (5)	−0.0031 (5)
C6	0.0265 (7)	0.0283 (7)	0.0258 (7)	−0.0094 (6)	0.0145 (6)	−0.0062 (5)
C7	0.0199 (6)	0.0273 (7)	0.0259 (7)	−0.0043 (5)	0.0076 (5)	−0.0063 (5)
C8	0.0209 (6)	0.0200 (6)	0.0190 (6)	−0.0034 (5)	0.0054 (5)	−0.0030 (5)
C9	0.0203 (6)	0.0142 (6)	0.0187 (6)	−0.0042 (5)	0.0067 (5)	−0.0044 (5)
C10	0.0208 (6)	0.0135 (6)	0.0188 (6)	−0.0030 (5)	0.0065 (5)	−0.0033 (5)
C11	0.0203 (6)	0.0158 (6)	0.0181 (6)	−0.0023 (5)	0.0064 (5)	−0.0019 (4)
C12	0.0227 (7)	0.0153 (6)	0.0198 (6)	−0.0026 (5)	0.0076 (5)	−0.0032 (5)
C13	0.0295 (7)	0.0232 (7)	0.0262 (7)	−0.0014 (5)	0.0143 (6)	−0.0012 (5)
C14	0.0183 (7)	0.0371 (8)	0.0394 (8)	−0.0031 (6)	0.0079 (6)	−0.0001 (6)
C15	0.0225 (7)	0.0191 (6)	0.0192 (6)	−0.0034 (5)	0.0104 (5)	−0.0025 (5)

Geometric parameters (Å, º) top

O1—N1	1.3844 (13)	C6—H6	0.9300
O1—C14	1.4442 (16)	C7—C8	1.3685 (18)
N1—C12	1.3559 (16)	C7—H7	0.9300
N1—C1	1.3784 (16)	C8—C9	1.4149 (18)
N2—C15	1.1529 (16)	C8—H8	0.9300
C1—C10	1.3958 (17)	C9—C10	1.4312 (17)
C1—C2	1.4054 (17)	C10—C11	1.4408 (16)
C2—C3	1.3631 (19)	C11—C12	1.3846 (18)
C2—H2	0.9300	C11—C15	1.4245 (18)
C3—C4	1.4311 (18)	C12—C13	1.4862 (17)
C3—H3	0.9300	C13—H13A	0.9600
C4—C5	1.4163 (18)	C13—H13B	0.9600
C4—C9	1.4292 (17)	C13—H13C	0.9600
C5—C6	1.3662 (19)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—C7	1.4106 (19)	C14—H14C	0.9600

N1—O1—C14	110.19 (9)	C9—C8—H8	119.5
C12—N1—C1	112.19 (10)	C8—C9—C4	118.80 (11)
C12—N1—O1	124.28 (10)	C8—C9—C10	124.02 (11)
C1—N1—O1	123.30 (10)	C4—C9—C10	117.16 (11)
N1—C1—C10	106.64 (11)	C1—C10—C9	119.12 (11)
N1—C1—C2	129.27 (11)	C1—C10—C11	106.30 (11)
C10—C1—C2	124.03 (12)	C9—C10—C11	134.51 (11)
C3—C2—C1	117.16 (11)	C12—C11—C15	123.07 (11)
C3—C2—H2	121.4	C12—C11—C10	108.38 (11)
C1—C2—H2	121.4	C15—C11—C10	128.54 (11)
C2—C3—C4	122.01 (12)	N1—C12—C11	106.49 (11)
C2—C3—H3	119.0	N1—C12—C13	122.83 (11)
C4—C3—H3	119.0	C11—C12—C13	130.67 (12)
C5—C4—C9	118.56 (11)	C12—C13—H13A	109.5
C5—C4—C3	120.91 (11)	C12—C13—H13B	109.5
C9—C4—C3	120.51 (11)	H13A—C13—H13B	109.5
C6—C5—C4	121.21 (12)	C12—C13—H13C	109.5
C6—C5—H5	119.4	H13A—C13—H13C	109.5
C4—C5—H5	119.4	H13B—C13—H13C	109.5
C5—C6—C7	120.10 (12)	O1—C14—H14A	109.5
C5—C6—H6	120.0	O1—C14—H14B	109.5
C7—C6—H6	120.0	H14A—C14—H14B	109.5
C8—C7—C6	120.40 (12)	O1—C14—H14C	109.5
C8—C7—H7	119.8	H14A—C14—H14C	109.5
C6—C7—H7	119.8	H14B—C14—H14C	109.5
C7—C8—C9	120.91 (12)	N2—C15—C11	179.39 (13)
C7—C8—H8	119.5

C14—O1—N1—C12	93.87 (13)	N1—C1—C10—C9	178.00 (10)
C14—O1—N1—C1	−92.15 (13)	C2—C1—C10—C9	0.53 (18)
C12—N1—C1—C10	−0.59 (13)	N1—C1—C10—C11	0.58 (12)
O1—N1—C1—C10	−175.22 (10)	C2—C1—C10—C11	−176.89 (11)
C12—N1—C1—C2	176.70 (12)	C8—C9—C10—C1	−179.17 (11)
O1—N1—C1—C2	2.08 (19)	C4—C9—C10—C1	−0.57 (16)
N1—C1—C2—C3	−177.49 (11)	C8—C9—C10—C11	−2.7 (2)
C10—C1—C2—C3	−0.62 (18)	C4—C9—C10—C11	175.95 (12)
C1—C2—C3—C4	0.78 (18)	C1—C10—C11—C12	−0.40 (13)
C2—C3—C4—C5	177.32 (11)	C9—C10—C11—C12	−177.24 (12)
C2—C3—C4—C9	−0.89 (18)	C1—C10—C11—C15	178.68 (11)
C9—C4—C5—C6	−1.41 (18)	C9—C10—C11—C15	1.8 (2)
C3—C4—C5—C6	−179.65 (11)	C1—N1—C12—C11	0.33 (13)
C4—C5—C6—C7	0.48 (19)	O1—N1—C12—C11	174.90 (10)
C5—C6—C7—C8	0.70 (19)	C1—N1—C12—C13	179.24 (11)
C6—C7—C8—C9	−0.91 (18)	O1—N1—C12—C13	−6.20 (18)
C7—C8—C9—C4	−0.04 (17)	C15—C11—C12—N1	−179.09 (10)
C7—C8—C9—C10	178.54 (11)	C10—C11—C12—N1	0.05 (13)
C5—C4—C9—C8	1.18 (17)	C15—C11—C12—C13	2.1 (2)
C3—C4—C9—C8	179.42 (10)	C10—C11—C12—C13	−178.73 (12)
C5—C4—C9—C10	−177.50 (10)	C12—C11—C15—N2	20 (14)
C3—C4—C9—C10	0.75 (17)	C10—C11—C15—N2	−159 (14)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg3ⁱ	0.93	2.65	3.3956 (15)	138

Symmetry code: (i) x, −y−1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂N₂O
M_r	236.27
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	113
a, b, c (Å)	18.663 (4), 7.3763 (15), 18.589 (4)
β (°)	113.46 (3)
V (Å³)	2347.6 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Rigaku Saturn CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.983, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	11412, 2060, 1858
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.094, 1.04
No. of reflections	2060
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.16

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C4–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg3ⁱ	0.93	2.65	3.3956 (15)	138

Symmetry code: (i) x, −y−1, z−1/2.

References

Du, Y. F., Chang, J. B., Reiner, J. & Zhao, K. (2008). J. Org. Chem. 73, 2007–2010. Web of Science CSD CrossRef PubMed CAS Google Scholar
Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536809052416

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