1-(2-Methyl­benz­yl)-1H-indole-3-carbaldehyde

Wu, Y.; Ren, W.; Wang, Q.; He, G.

doi:10.1107/S1600536812010306

organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page o1151

doi:10.1107/S1600536812010306

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1-(2-Methylbenzyl)-1H-indole-3-carbaldehyde

Yang Wu,^a Wen Ren,^b Qiang Wang ^b and Gu He ^c ^*

^aState Key Laboratory of Biotherapy and Cancer Center, West China Hospital, West China Medical School, Sichuan University, Chengdu 610041, People's Republic of China, ^bWest China School of Pharmacy, Sichuan University, Chengdu 610041, People's Republic of China, and ^cState Key Laboratory of Biotherapy and Cancer Center, West China Hospital, West China Medical School, Sichuan University, Chengdu 610041, People's Republic of China
^*Correspondence e-mail: hegu@scu.edu.cn

(Received 6 March 2012; accepted 8 March 2012; online 24 March 2012)

In the title compound, C₁₇H₁₅NO, the benzene ring and the indole system are almost perpendicular, making a dihedral angle of 87.82 (6)°. The crystal packing is stabilized by C—H⋯O and π–π stacking interactions with centroid–centroid distances of 3.592 (4) Å between the pyrrole and the benzene rings in the indole systems of neighboring molecules.

Related literature

For general background to the chemistry and anti-inflammatory activity of carboxylic acid derivatives, see: Andreani et al. (1994 ).

Experimental

Crystal data

C₁₇H₁₅NO
M_r = 249.30
Monoclinic, P 2₁ /c
a = 10.5251 (3) Å
b = 15.4352 (5) Å
c = 8.2335 (2) Å
β = 99.214 (3)°
V = 1320.33 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.28 × 0.25 × 0.20 mm

Data collection

Agilent Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.981, T_max = 1.000
5468 measured reflections
2699 independent reflections
1928 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.117
S = 1.04
2699 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯O1ⁱ	0.93	2.56	3.418 (2)	154
Symmetry code: (i) x, y, z+1.

Data collection: CrysAlis PRO (Agilent, 2011); 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: OLEX2 (Dolomanov, 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812010306/bt5840sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812010306/bt5840Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812010306/bt5840Isup3.cml

checkCIF report

Comment top

1-(2-Methyl-benzyl)-1H-indole-3-carbaldehyde is of great importance owing to its wide biological properties (Andreani et al., 1994). The title compound is one of the key intermediates in our synthetic investigations of antibacterial drugs. We report here its crystal structure.

In the title compound, C₁₇H₁₅NO, as shown in Fig 1, the benzene ring with the methyl group in ortho position and the indole system are almost perpendicular, making dihedral angle of 87.82 (6)°. A combination of intermolecular C-H···O and π–π packing interaction plays an important role in the connection of neighbouring molecules. The centroid-centroid distance between the pyrrole ring and the benzene ring in the indole system of the neighbouring molecule is 3.592 (4) Å (symmetry operator: -x, -y, -z).

Related literature top

For general background to the chemistry and anti-inflammatory activity of indole carboxylic acid derivatives, see: Andreani et al. (1994).

Experimental top

1H-indole-3-carbaldehyde(14 mmol) was dissolved in dry DMF(25 ml)and treated portionwise,under stirring, with 20 mmol NaH. The mixture was stirred at room temperature for 10 min and treated with 20 mmol of 1-chloromethyl-2-methyl-benzene. After 1 h at 90°C under stirring, the mixture was poured onto ice. The resulting precipitate was collected by filtration and crystallized from ethanol with a yield of 70%. Crystals suitable for X-ray analysis were obtained by slow evaporation from a solution of dichloromethane.

Structure description top

For general background to the chemistry and anti-inflammatory activity of indole carboxylic acid derivatives, see: Andreani et al. (1994).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov, 2009); software used to prepare material for publication: OLEX2 (Dolomanov, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A packing diagram of the title compound.

1-(2-Methylbenzyl)-1H-indole-3-carbaldehyde top

Crystal data top

C₁₇H₁₅NO	F(000) = 528
M_r = 249.30	D_x = 1.254 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
a = 10.5251 (3) Å	Cell parameters from 1937 reflections
b = 15.4352 (5) Å	θ = 3.2–29.1°
c = 8.2335 (2) Å	µ = 0.08 mm⁻¹
β = 99.214 (3)°	T = 293 K
V = 1320.33 (7) Å³	Block, colorless
Z = 4	0.28 × 0.25 × 0.20 mm

Data collection top

Agilent Xcalibur Eos diffractometer	2699 independent reflections
Radiation source: fine-focus sealed tube	1928 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
Detector resolution: 16.0874 pixels mm^-1	θ_max = 26.4°, θ_min = 3.2°
ω scans	h = −11→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −11→19
T_min = 0.981, T_max = 1.000	l = −10→4
5468 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0449P)² + 0.2065P] where P = (F_o² + 2F_c²)/3
2699 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₇H₁₅NO	V = 1320.33 (7) Å³
M_r = 249.30	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.5251 (3) Å	µ = 0.08 mm⁻¹
b = 15.4352 (5) Å	T = 293 K
c = 8.2335 (2) Å	0.28 × 0.25 × 0.20 mm
β = 99.214 (3)°

Data collection top

Agilent Xcalibur Eos diffractometer	2699 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1928 reflections with I > 2σ(I)
T_min = 0.981, T_max = 1.000	R_int = 0.016
5468 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.04	Δρ_max = 0.13 e Å⁻³
2699 reflections	Δρ_min = −0.17 e Å⁻³
173 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	0.02058 (15)	0.14964 (11)	−0.33644 (17)	0.0895 (5)
N1	0.21128 (12)	0.01830 (9)	0.14071 (15)	0.0439 (3)
C1	0.18887 (13)	−0.04418 (11)	0.01839 (19)	0.0404 (4)
C2	0.13295 (13)	−0.00278 (11)	−0.12762 (19)	0.0415 (4)
C3	0.12187 (14)	0.08699 (11)	−0.0886 (2)	0.0457 (4)
C4	0.17018 (15)	0.09542 (11)	0.0760 (2)	0.0475 (4)
H4	0.1739	0.1472	0.1344	0.057*
C5	0.10025 (15)	−0.05289 (13)	−0.2699 (2)	0.0506 (4)
H5	0.0639	−0.0273	−0.3687	0.061*
C6	0.12281 (16)	−0.14068 (13)	−0.2611 (2)	0.0573 (5)
H6	0.1010	−0.1744	−0.3549	0.069*
C7	0.17749 (16)	−0.17975 (12)	−0.1149 (2)	0.0567 (5)
H7	0.1910	−0.2393	−0.1126	0.068*
C8	0.21221 (15)	−0.13246 (11)	0.0266 (2)	0.0503 (4)
H8	0.2499	−0.1587	0.1242	0.060*
C9	0.06793 (18)	0.15646 (14)	−0.1918 (3)	0.0642 (5)
H9	0.0690	0.2113	−0.1449	0.077*
C10	0.26384 (17)	0.00142 (12)	0.31387 (19)	0.0536 (5)
H10A	0.3153	−0.0510	0.3210	0.064*
H10B	0.1933	−0.0082	0.3745	0.064*
C11	0.34564 (15)	0.07493 (11)	0.39236 (19)	0.0455 (4)
C12	0.46514 (15)	0.09284 (11)	0.34816 (19)	0.0448 (4)
C13	0.53745 (17)	0.15965 (12)	0.4283 (2)	0.0565 (5)
H13	0.6176	0.1721	0.4002	0.068*
C14	0.4941 (2)	0.20792 (14)	0.5479 (2)	0.0679 (6)
H14	0.5445	0.2525	0.5997	0.082*
C15	0.3765 (2)	0.19041 (15)	0.5909 (3)	0.0744 (6)
H15	0.3467	0.2228	0.6722	0.089*
C16	0.30237 (18)	0.12415 (14)	0.5125 (2)	0.0637 (5)
H16	0.2221	0.1125	0.5411	0.076*
C17	0.51550 (17)	0.04237 (15)	0.2160 (2)	0.0666 (6)
H17A	0.5075	−0.0185	0.2360	0.100*
H17B	0.6044	0.0565	0.2168	0.100*
H17C	0.4667	0.0568	0.1108	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1027 (11)	0.1071 (13)	0.0562 (9)	0.0489 (10)	0.0050 (8)	0.0189 (9)
N1	0.0436 (7)	0.0468 (8)	0.0395 (7)	−0.0044 (6)	0.0014 (6)	0.0004 (7)
C1	0.0344 (8)	0.0448 (10)	0.0419 (9)	−0.0048 (7)	0.0059 (6)	−0.0003 (8)
C2	0.0307 (7)	0.0519 (10)	0.0418 (9)	−0.0009 (7)	0.0059 (6)	0.0016 (8)
C3	0.0377 (8)	0.0520 (11)	0.0471 (9)	0.0042 (7)	0.0054 (7)	0.0049 (8)
C4	0.0461 (9)	0.0446 (10)	0.0515 (10)	−0.0020 (7)	0.0070 (8)	−0.0009 (8)
C5	0.0386 (8)	0.0719 (13)	0.0404 (9)	−0.0027 (8)	0.0031 (7)	−0.0013 (9)
C6	0.0509 (10)	0.0663 (13)	0.0550 (11)	−0.0111 (9)	0.0098 (8)	−0.0169 (10)
C7	0.0570 (10)	0.0472 (11)	0.0663 (12)	−0.0060 (8)	0.0109 (9)	−0.0063 (9)
C8	0.0495 (9)	0.0482 (11)	0.0523 (10)	−0.0042 (8)	0.0052 (8)	0.0054 (9)
C9	0.0626 (12)	0.0655 (13)	0.0659 (13)	0.0204 (10)	0.0145 (10)	0.0106 (11)
C10	0.0586 (10)	0.0626 (12)	0.0381 (9)	−0.0110 (9)	0.0031 (8)	0.0043 (8)
C11	0.0486 (9)	0.0514 (10)	0.0348 (8)	−0.0002 (8)	0.0020 (7)	0.0014 (8)
C12	0.0459 (9)	0.0520 (10)	0.0345 (8)	0.0019 (8)	0.0004 (7)	0.0041 (8)
C13	0.0511 (10)	0.0644 (12)	0.0505 (10)	−0.0082 (9)	−0.0028 (8)	0.0026 (10)
C14	0.0765 (13)	0.0592 (13)	0.0622 (12)	−0.0081 (11)	−0.0073 (11)	−0.0119 (11)
C15	0.0856 (15)	0.0753 (15)	0.0612 (13)	0.0110 (12)	0.0082 (11)	−0.0251 (11)
C16	0.0579 (11)	0.0806 (15)	0.0541 (11)	0.0017 (10)	0.0133 (9)	−0.0112 (10)
C17	0.0572 (11)	0.0863 (16)	0.0584 (12)	0.0029 (10)	0.0161 (9)	−0.0093 (11)

Geometric parameters (Å, º) top

O1—C9	1.220 (2)	C9—H9	0.9300
N1—C1	1.387 (2)	C10—H10A	0.9700
N1—C4	1.347 (2)	C10—H10B	0.9700
N1—C10	1.4677 (19)	C10—C11	1.506 (2)
C1—C2	1.405 (2)	C11—C12	1.392 (2)
C1—C8	1.384 (2)	C11—C16	1.381 (2)
C2—C3	1.431 (2)	C12—C13	1.385 (2)
C2—C5	1.400 (2)	C12—C17	1.502 (2)
C3—C4	1.375 (2)	C13—H13	0.9300
C3—C9	1.428 (2)	C13—C14	1.370 (3)
C4—H4	0.9300	C14—H14	0.9300
C5—H5	0.9300	C14—C15	1.367 (3)
C5—C6	1.376 (3)	C15—H15	0.9300
C6—H6	0.9300	C15—C16	1.382 (3)
C6—C7	1.386 (3)	C16—H16	0.9300
C7—H7	0.9300	C17—H17A	0.9600
C7—C8	1.374 (2)	C17—H17B	0.9600
C8—H8	0.9300	C17—H17C	0.9600

C1—N1—C10	125.15 (14)	N1—C10—H10A	109.1
C4—N1—C1	108.69 (13)	N1—C10—H10B	109.1
C4—N1—C10	126.06 (14)	N1—C10—C11	112.57 (14)
N1—C1—C2	107.72 (14)	H10A—C10—H10B	107.8
C8—C1—N1	129.84 (15)	C11—C10—H10A	109.1
C8—C1—C2	122.44 (15)	C11—C10—H10B	109.1
C1—C2—C3	106.65 (14)	C12—C11—C10	121.05 (15)
C5—C2—C1	118.56 (16)	C16—C11—C10	119.37 (16)
C5—C2—C3	134.79 (16)	C16—C11—C12	119.57 (16)
C4—C3—C2	106.38 (14)	C11—C12—C17	121.66 (15)
C4—C3—C9	124.34 (17)	C13—C12—C11	118.30 (15)
C9—C3—C2	129.24 (16)	C13—C12—C17	120.04 (16)
N1—C4—C3	110.55 (15)	C12—C13—H13	119.1
N1—C4—H4	124.7	C14—C13—C12	121.77 (17)
C3—C4—H4	124.7	C14—C13—H13	119.1
C2—C5—H5	120.6	C13—C14—H14	120.1
C6—C5—C2	118.87 (16)	C15—C14—C13	119.88 (18)
C6—C5—H5	120.6	C15—C14—H14	120.1
C5—C6—H6	119.4	C14—C15—H15	120.3
C5—C6—C7	121.23 (17)	C14—C15—C16	119.49 (18)
C7—C6—H6	119.4	C16—C15—H15	120.3
C6—C7—H7	119.3	C11—C16—C15	121.00 (18)
C8—C7—C6	121.48 (18)	C11—C16—H16	119.5
C8—C7—H7	119.3	C15—C16—H16	119.5
C1—C8—H8	121.3	C12—C17—H17A	109.5
C7—C8—C1	117.41 (16)	C12—C17—H17B	109.5
C7—C8—H8	121.3	C12—C17—H17C	109.5
O1—C9—C3	125.3 (2)	H17A—C17—H17B	109.5
O1—C9—H9	117.4	H17A—C17—H17C	109.5
C3—C9—H9	117.4	H17B—C17—H17C	109.5

N1—C1—C2—C3	−0.28 (16)	C5—C2—C3—C9	1.2 (3)
N1—C1—C2—C5	−179.55 (13)	C5—C6—C7—C8	−0.5 (3)
N1—C1—C8—C7	178.63 (15)	C6—C7—C8—C1	0.9 (2)
N1—C10—C11—C12	−69.9 (2)	C8—C1—C2—C3	179.02 (14)
N1—C10—C11—C16	111.41 (18)	C8—C1—C2—C5	−0.3 (2)
C1—N1—C4—C3	−0.86 (18)	C9—C3—C4—N1	178.46 (15)
C1—N1—C10—C11	147.04 (15)	C10—N1—C1—C2	177.28 (13)
C1—C2—C3—C4	−0.23 (16)	C10—N1—C1—C8	−1.9 (2)
C1—C2—C3—C9	−177.87 (16)	C10—N1—C4—C3	−177.41 (13)
C1—C2—C5—C6	0.6 (2)	C10—C11—C12—C13	−178.10 (15)
C2—C1—C8—C7	−0.5 (2)	C10—C11—C12—C17	2.5 (2)
C2—C3—C4—N1	0.67 (17)	C10—C11—C16—C15	178.00 (18)
C2—C3—C9—O1	0.0 (3)	C11—C12—C13—C14	−0.3 (3)
C2—C5—C6—C7	−0.3 (2)	C12—C11—C16—C15	−0.7 (3)
C3—C2—C5—C6	−178.37 (16)	C12—C13—C14—C15	0.1 (3)
C4—N1—C1—C2	0.69 (16)	C13—C14—C15—C16	−0.2 (3)
C4—N1—C1—C8	−178.54 (15)	C14—C15—C16—C11	0.5 (3)
C4—N1—C10—C11	−37.0 (2)	C16—C11—C12—C13	0.5 (2)
C4—C3—C9—O1	−177.28 (17)	C16—C11—C12—C17	−178.81 (16)
C5—C2—C3—C4	178.87 (16)	C17—C12—C13—C14	179.10 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O1ⁱ	0.93	2.56	3.418 (2)	154

Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₅NO
M_r	249.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	10.5251 (3), 15.4352 (5), 8.2335 (2)
β (°)	99.214 (3)
V (Å³)	1320.33 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.28 × 0.25 × 0.20

Data collection
Diffractometer	Agilent Xcalibur Eos
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.981, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5468, 2699, 1928
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.117, 1.04
No. of reflections	2699
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.17

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O1ⁱ	0.9300	2.5600	3.418 (2)	154.00

Symmetry code: (i) x, y, z+1.

Acknowledgements

We thank the Analytical and Testing Center of Sichuan University for the X-ray measurements.

References

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