1-Vinyl-1H-indole-3-carbaldehyde

Selvanayagam, S.; Sridhar, B.; Ravikumar, K.; Kathiravan, S.; Raghunathan, R.

doi:10.1107/S160053680801547X

organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1163

doi:10.1107/S160053680801547X

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1-Vinyl-1H-indole-3-carbaldehyde

S. Selvanayagam,^a ^* B. Sridhar,^b K. Ravikumar,^b S. Kathiravan ^c and R. Raghunathan ^c

^aDepartment of Physics, Kalasalingam University, Krishnankoil 626 190, India, ^bLaboratory of X-ray Crystallography, Indian Institute of Chemical Technology, Hyderabad 500 007, India, and ^cDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: s_selvanayagam@rediffmail.com

(Received 19 May 2008; accepted 22 May 2008; online 30 May 2008)

In the title compound, C₁₁H₉NO, the C and O atoms of the attached carbaldehyde group deviate by just 0.052 (2) and 0.076 (1) Å, respectively, from the mean plane of the indole ring system. In addition to van der Waals forces, the molecular packing is stabilized by C—H⋯O hydrogen bonds, which form a C(7) chain motif, and π–π interactions (centroid–centroid distance 3.637 Å) between the pyrrole and benzene rings of the indole ring system.

Related literature

For related literature, see: Padwa et al. (1999 ); Mathiesen et al. (2005 ); Grinev et al. (1984 ); Gadaginamath & Patil (1999 ); Rodriguez et al. (1985 ); Karthick et al. (2005 ); Selvanayagam et al. (2005 ); Sonar et al. (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₉NO
M_r = 171.19
Monoclinic, P 2₁ /n
a = 8.3200 (5) Å
b = 8.1490 (5) Å
c = 13.1620 (7) Å
β = 99.952 (1)°
V = 878.95 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 (2) K
0.24 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: none
9730 measured reflections
2072 independent reflections
1823 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.127
S = 1.05
2072 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1ⁱ	0.93	2.51	3.390 (2)	159
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680801547X/bt2714sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680801547X/bt2714Isup2.hkl

checkCIF report

Comment top

Indoles and their derivatives have been interest for many years, since large number of natural products contain indole systems and they are found in a number of pharmaceutical products, fragrances and dyes (Padwa et al., 1999). Indole derivatives are identified as interfering with a G protein-independent signaling pathway of the CRTH2 receptor (Mathiesen et al., 2005). These derivatives possess antidepressant (Grinev et al., 1984), anti-microbial (Gadaginamath & Patil, 1999) and anti-inflammatory (Rodriguez et al., 1985) activities. In view of its importance, we have undertaken the single-crystal X-ray diffraction study and report here its results.

The X-ray study confirmed the molecular structure and atomic connectivity for (I), as illustrated in Fig. 1. The geometry of the indole ring system is comparable to those reported for other indole derivatives (Karthick et al., 2005; Selvanayagam et al., 2005; Sonar et al., 2005). The bond length of C9—C10 [1.284 (2) Å] confirms the double bond character (Allen et al., 1987). The sum of the angles at N1 of the indole ring (360°) is in accordance with sp² hybridization.

The indole ring is planar with a maximum deviation of 0.017 (1) Å for atom C8. The carbaldehyde group atoms C11 and O1 deviate 0.052 (2) and 0.076 (1) Å, respectively from the best plane of the indole ring.

In addition to the van der Waals forces, the molecular packing is stabilized by intermolecular C—H···O hydrogen bond (Table 2). Atom H9 of C9 forms a intermolecular hydrogen bond with oxygen atom O1 forming a C(7) chain motif of C—H···O hydrogen bond along the diagonal of ac plane (Fig. 2). In addition to this a weak π···π interaction between the pyrrole ring (N1/C1/C6—C8) at (x,y,z) and benzene ring (C1—C6) at (1 -x, -y), -z) stabilizes the molecular packing. The centroid-to-centroid distance is 3.637Å.

Related literature top

For related literature, see: Padwa et al. (1999); Mathiesen et al. (2005); Grinev et al. (1984); Gadaginamath & Patil (1999); Rodriguez et al. (1985); Karthick et al. (2005); Selvanayagam et al. (2005); Sonar et al. (2005). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of N-vinylindole (0.05 mol) and DMF (0.15 mol) was stirred with POCl₃ (32.3 ml). The reaction mixture was poured into ice water (300 ml) and stirred for 30minutes at less than 10° C. The precipitated solid was collected by filtration and washed well water (100 ml). In order to get the diffraction quality crystals, the compound was recrystallized from ethyl acetate.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. The structure and atom-numbering scheme for the title compound; displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. Molecular packing of the title compound viewed down the b axis; H-bonds are shown as dashed lines. For clarity, H atoms, not involved in hydrogen bonds, have been omitted.

1-Vinyl-1H-indole-3-carbaldehyde top

Crystal data top

C₁₁H₉NO	F(000) = 360
M_r = 171.19	D_x = 1.294 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4554 reflections
a = 8.3200 (5) Å	θ = 2.1–23.6°
b = 8.1490 (5) Å	µ = 0.08 mm⁻¹
c = 13.1620 (7) Å	T = 293 K
β = 99.952 (1)°	Block, colourless
V = 878.95 (9) Å³	0.24 × 0.22 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1823 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
Graphite monochromator	θ_max = 28.0°, θ_min = 3.0°
ω scans	h = −10→10
9730 measured reflections	k = −10→10
2072 independent reflections	l = −17→16

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0665P)² + 0.1375P] where P = (F_o² + 2F_c²)/3
2072 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₁H₉NO	V = 878.95 (9) Å³
M_r = 171.19	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.3200 (5) Å	µ = 0.08 mm⁻¹
b = 8.1490 (5) Å	T = 293 K
c = 13.1620 (7) Å	0.24 × 0.22 × 0.20 mm
β = 99.952 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1823 reflections with I > 2σ(I)
9730 measured reflections	R_int = 0.020
2072 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.05	Δρ_max = 0.21 e Å⁻³
2072 reflections	Δρ_min = −0.19 e Å⁻³
118 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	0.81283 (15)	0.20464 (18)	−0.13362 (9)	0.0826 (4)
N1	0.41791 (12)	0.24005 (13)	0.07004 (7)	0.0469 (3)
C1	0.54641 (14)	0.14623 (13)	0.12226 (8)	0.0424 (3)
C2	0.56155 (16)	0.06833 (16)	0.21713 (9)	0.0505 (3)
H2	0.4800	0.0748	0.2572	0.061*
C3	0.70276 (18)	−0.01899 (17)	0.24918 (10)	0.0581 (3)
H3	0.7166	−0.0736	0.3121	0.070*
C4	0.82544 (17)	−0.02764 (17)	0.18966 (11)	0.0594 (4)
H4	0.9197	−0.0870	0.2139	0.071*
C5	0.80997 (15)	0.04980 (16)	0.09564 (10)	0.0527 (3)
H5	0.8925	0.0434	0.0563	0.063*
C6	0.66781 (14)	0.13815 (13)	0.06061 (8)	0.0431 (3)
C7	0.60762 (15)	0.23003 (15)	−0.03148 (9)	0.0480 (3)
C8	0.45684 (16)	0.28725 (16)	−0.02188 (9)	0.0503 (3)
H8	0.3901	0.3497	−0.0712	0.060*
C9	0.27187 (17)	0.27412 (19)	0.10596 (12)	0.0615 (4)
H9	0.2701	0.2521	0.1751	0.074*
C10	0.14066 (19)	0.3327 (2)	0.05257 (15)	0.0779 (5)
H10A	0.1365	0.3567	−0.0169	0.094*
H10B	0.0498	0.3511	0.0834	0.094*
C11	0.68162 (19)	0.2565 (2)	−0.12120 (11)	0.0621 (4)
H11	0.6233	0.3191	−0.1742	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0720 (7)	0.1185 (10)	0.0649 (7)	0.0021 (6)	0.0336 (6)	0.0075 (6)
N1	0.0474 (5)	0.0518 (6)	0.0428 (5)	0.0032 (4)	0.0110 (4)	−0.0026 (4)
C1	0.0457 (6)	0.0418 (5)	0.0396 (5)	−0.0022 (4)	0.0075 (4)	−0.0069 (4)
C2	0.0595 (7)	0.0521 (7)	0.0417 (6)	−0.0035 (5)	0.0136 (5)	−0.0023 (5)
C3	0.0707 (8)	0.0549 (7)	0.0464 (6)	0.0007 (6)	0.0035 (6)	0.0051 (5)
C4	0.0562 (7)	0.0544 (7)	0.0641 (8)	0.0080 (6)	0.0011 (6)	0.0007 (6)
C5	0.0475 (6)	0.0527 (7)	0.0591 (7)	0.0000 (5)	0.0129 (5)	−0.0070 (5)
C6	0.0472 (6)	0.0418 (6)	0.0411 (5)	−0.0053 (4)	0.0102 (4)	−0.0072 (4)
C7	0.0543 (7)	0.0486 (6)	0.0425 (6)	−0.0046 (5)	0.0124 (5)	−0.0023 (5)
C8	0.0566 (7)	0.0513 (7)	0.0427 (6)	0.0017 (5)	0.0079 (5)	0.0021 (5)
C9	0.0564 (8)	0.0736 (9)	0.0586 (8)	0.0089 (6)	0.0209 (6)	−0.0013 (6)
C10	0.0580 (9)	0.0892 (12)	0.0894 (12)	0.0170 (8)	0.0205 (8)	0.0036 (9)
C11	0.0670 (8)	0.0743 (9)	0.0481 (7)	−0.0059 (7)	0.0185 (6)	0.0041 (6)

Geometric parameters (Å, º) top

O1—C11	1.2079 (19)	C5—C6	1.3933 (17)
N1—C8	1.3610 (16)	C5—H5	0.9300
N1—C1	1.3949 (15)	C6—C7	1.4390 (17)
N1—C9	1.4055 (16)	C7—C8	1.3645 (18)
C1—C2	1.3869 (16)	C7—C11	1.4393 (18)
C1—C6	1.4023 (16)	C8—H8	0.9300
C2—C3	1.3760 (19)	C9—C10	1.284 (2)
C2—H2	0.9300	C9—H9	0.9300
C3—C4	1.392 (2)	C10—H10A	0.9300
C3—H3	0.9300	C10—H10B	0.9300
C4—C5	1.3751 (19)	C11—H11	0.9300
C4—H4	0.9300

C8—N1—C1	108.24 (10)	C5—C6—C1	119.20 (11)
C8—N1—C9	126.55 (12)	C5—C6—C7	134.39 (11)
C1—N1—C9	125.17 (11)	C1—C6—C7	106.40 (10)
C2—C1—N1	129.57 (11)	C8—C7—C6	106.95 (10)
C2—C1—C6	122.48 (11)	C8—C7—C11	123.72 (13)
N1—C1—C6	107.94 (10)	C6—C7—C11	129.29 (12)
C3—C2—C1	116.91 (12)	N1—C8—C7	110.46 (11)
C3—C2—H2	121.5	N1—C8—H8	124.8
C1—C2—H2	121.5	C7—C8—H8	124.8
C2—C3—C4	121.60 (12)	C10—C9—N1	126.30 (15)
C2—C3—H3	119.2	C10—C9—H9	116.8
C4—C3—H3	119.2	N1—C9—H9	116.8
C5—C4—C3	121.31 (12)	C9—C10—H10A	120.0
C5—C4—H4	119.3	C9—C10—H10B	120.0
C3—C4—H4	119.3	H10A—C10—H10B	120.0
C4—C5—C6	118.49 (12)	O1—C11—C7	125.68 (15)
C4—C5—H5	120.8	O1—C11—H11	117.2
C6—C5—H5	120.8	C7—C11—H11	117.2

C8—N1—C1—C2	−178.34 (12)	N1—C1—C6—C7	−0.32 (12)
C9—N1—C1—C2	−0.3 (2)	C5—C6—C7—C8	178.96 (13)
C8—N1—C1—C6	0.77 (13)	C1—C6—C7—C8	−0.24 (13)
C9—N1—C1—C6	178.86 (12)	C5—C6—C7—C11	1.3 (2)
N1—C1—C2—C3	178.96 (11)	C1—C6—C7—C11	−177.94 (13)
C6—C1—C2—C3	−0.04 (18)	C1—N1—C8—C7	−0.95 (14)
C1—C2—C3—C4	0.56 (19)	C9—N1—C8—C7	−179.00 (12)
C2—C3—C4—C5	−0.6 (2)	C6—C7—C8—N1	0.73 (14)
C3—C4—C5—C6	0.0 (2)	C11—C7—C8—N1	178.60 (12)
C4—C5—C6—C1	0.47 (17)	C8—N1—C9—C10	11.7 (3)
C4—C5—C6—C7	−178.65 (12)	C1—N1—C9—C10	−166.00 (16)
C2—C1—C6—C5	−0.47 (17)	C8—C7—C11—O1	−178.09 (15)
N1—C1—C6—C5	−179.66 (10)	C6—C7—C11—O1	−0.7 (3)
C2—C1—C6—C7	178.87 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.93	2.51	3.390 (2)	159

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₉NO
M_r	171.19
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.3200 (5), 8.1490 (5), 13.1620 (7)
β (°)	99.952 (1)
V (Å³)	878.95 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.24 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9730, 2072, 1823
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.127, 1.05
No. of reflections	2072
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PARST (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.93	2.51	3.390 (2)	159

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

Acknowledgements

SS thanks the Vice Chancellor and management of Kalasalingam University, Anand Nagar, Krishnankoil, for their support and encouragement.

References

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