5-Methyl-1H-indole-3-carbaldehyde

Ismail, S.S.; Khaledi, H.; Mohd Ali, H.

doi:10.1107/S1600536812034873

organic compounds

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Volume 68| Part 9| September 2012| Page o2691

doi:10.1107/S1600536812034873

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5-Methyl-1H-indole-3-carbaldehyde

Sharifah Shafiqah Ismail,^a Hamid Khaledi ^a ^* and Hapipah Mohd Ali ^a

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: hamid.khaledi@gmail.com

(Received 4 August 2012; accepted 7 August 2012; online 11 August 2012)

The title molecule, C₁₀H₉NO, is almost planar with an r.m.s. deviation for all non-H atoms of 0.0115 Å. In the crystal, molecules are connected through N—H⋯O hydrogen bonds into chains running along [021]. The chains are further connected via C—H⋯π interactions, forming layers in the bc plane.

Related literature

For the structure of 1H-indole-3-carbaldehyde, see: Ng (2007 ) and for the structure of 6-bromo-1H-indole-3-carbaldehyde, see: Johnson et al. (2009 ).

Experimental

Crystal data

C₁₀H₉NO
M_r = 159.18
Orthorhombic, P c a 2₁
a = 16.9456 (19) Å
b = 5.7029 (6) Å
c = 8.6333 (9) Å
V = 834.31 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.47 × 0.15 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.962, T_max = 0.996
5499 measured reflections
1147 independent reflections
717 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.107
S = 0.98
1147 reflections
113 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N1/C1/C2/C3/C8 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.93 (3)	1.90 (3)	2.818 (3)	169 (3)
C9—H9⋯Cgⁱⁱ	0.93	2.91	3.312 (3)	107
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-1, z-{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812034873/zl2498sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812034873/zl2498Isup2.hkl

checkCIF report

Comment top

The structure of the title compound is isomorphous with that of 1H-indole-3-carbaldehyde (Ng, 2007). The planar molecules are connected via N—H···O hydrogen bonds (Table 1) into chains in the [021] direction. The chains are further linked through C—H···π interactions (Table 1) to form layers in the bc plane. The structure of 6-bromo-1H-indole-3-carbaldehyde (Johnson et al., 2009) exhibits similar N—H···O bonded chains, however, further supramolecular aggregation by Br-involved interactions is observed.

Related literature top

For the structure of 1H-indole-3-carbaldehyde, see: Ng (2007) and for the structure of 6-bromo-1H-indole-3-carbaldehyde, see: Johnson et al. (2009).

Experimental top

The title crystals were obtained by slow evaporation of an ethanolic solution of the commercially available 5-methylindole-3-carboxaldehyde at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound showing thermal ellipsoids at the 30% prbability level. Hydrogen spheres are drawn with an arbitrary radius.
	Fig. 2. Crystal packing view looking down the a axis, thus showing the two-dimensional-supramolecular structure formed by N—H···O and C—H···π interactions (dashed lines).

5-Methyl-1H-indole-3-carbaldehyde top

Crystal data top

C₁₀H₉NO	F(000) = 336
M_r = 159.18	D_x = 1.267 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1172 reflections
a = 16.9456 (19) Å	θ = 2.4–22.1°
b = 5.7029 (6) Å	µ = 0.08 mm⁻¹
c = 8.6333 (9) Å	T = 296 K
V = 834.31 (15) Å³	Lath, yellow
Z = 4	0.47 × 0.15 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	1147 independent reflections
Radiation source: fine-focus sealed tube	717 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ϕ and ω scans	θ_max = 28.8°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→13
T_min = 0.962, T_max = 0.996	k = −7→7
5499 measured reflections	l = −11→11

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0596P)²] where P = (F_o² + 2F_c²)/3
1147 reflections	(Δ/σ)_max < 0.001
113 parameters	Δρ_max = 0.12 e Å⁻³
1 restraint	Δρ_min = −0.14 e Å⁻³

Crystal data top

C₁₀H₉NO	V = 834.31 (15) Å³
M_r = 159.18	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 16.9456 (19) Å	µ = 0.08 mm⁻¹
b = 5.7029 (6) Å	T = 296 K
c = 8.6333 (9) Å	0.47 × 0.15 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	1147 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	717 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.996	R_int = 0.039
5499 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.12 e Å⁻³
1147 reflections	Δρ_min = −0.14 e Å⁻³
113 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	0.27204 (11)	1.0610 (3)	0.6573 (2)	0.0742 (6)
N1	0.29282 (16)	0.4126 (4)	0.3481 (3)	0.0760 (7)
H1N	0.2766 (15)	0.285 (5)	0.290 (5)	0.091*
C1	0.2435 (2)	0.5303 (4)	0.4384 (3)	0.0717 (8)
H1	0.1913	0.4879	0.4563	0.086*
C2	0.27969 (14)	0.7233 (4)	0.5018 (3)	0.0587 (6)
C3	0.35916 (14)	0.7227 (4)	0.4414 (3)	0.0535 (6)
C4	0.42432 (15)	0.8710 (4)	0.4561 (3)	0.0554 (6)
H4	0.4212	1.0036	0.5185	0.066*
C5	0.49316 (16)	0.8208 (4)	0.3782 (3)	0.0638 (7)
C6	0.49673 (18)	0.6225 (5)	0.2839 (4)	0.0785 (8)
H6	0.5434	0.5904	0.2311	0.094*
C7	0.4341 (2)	0.4736 (5)	0.2661 (3)	0.0766 (8)
H7	0.4377	0.3422	0.2026	0.092*
C8	0.36502 (18)	0.5241 (4)	0.3453 (3)	0.0626 (7)
C9	0.24192 (16)	0.8851 (4)	0.6026 (3)	0.0640 (6)
H9	0.1897	0.8544	0.6292	0.077*
C10	0.56347 (18)	0.9773 (6)	0.3966 (4)	0.0860 (10)
H10A	0.5654	1.0866	0.3121	0.129*
H10B	0.6107	0.8842	0.3969	0.129*
H10C	0.5595	1.0615	0.4926	0.129*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0843 (15)	0.0640 (9)	0.0743 (12)	0.0106 (9)	0.0086 (10)	−0.0101 (9)
N1	0.109 (2)	0.0565 (10)	0.0622 (13)	−0.0129 (12)	−0.0146 (15)	−0.0053 (11)
C1	0.0820 (19)	0.0660 (13)	0.0671 (17)	−0.0143 (15)	−0.0109 (17)	0.0081 (14)
C2	0.0722 (18)	0.0533 (11)	0.0508 (12)	−0.0012 (11)	−0.0030 (12)	0.0033 (10)
C3	0.0668 (17)	0.0499 (10)	0.0440 (11)	0.0056 (10)	−0.0070 (11)	−0.0013 (10)
C4	0.0639 (16)	0.0528 (10)	0.0495 (12)	0.0026 (11)	−0.0052 (12)	−0.0003 (10)
C5	0.0640 (18)	0.0699 (14)	0.0575 (14)	0.0141 (12)	−0.0022 (13)	0.0073 (13)
C6	0.081 (2)	0.0869 (18)	0.0678 (16)	0.0295 (15)	0.0074 (16)	0.0032 (15)
C7	0.105 (2)	0.0657 (14)	0.0590 (16)	0.0237 (16)	0.0008 (17)	−0.0133 (12)
C8	0.089 (2)	0.0488 (10)	0.0502 (13)	0.0051 (12)	−0.0112 (14)	−0.0021 (11)
C9	0.0662 (17)	0.0683 (13)	0.0574 (14)	0.0083 (14)	0.0013 (13)	0.0124 (13)
C10	0.068 (2)	0.102 (2)	0.088 (2)	0.0008 (17)	0.0032 (16)	0.0136 (17)

Geometric parameters (Å, º) top

O1—C9	1.221 (3)	C4—H4	0.9300
N1—C1	1.326 (4)	C5—C6	1.395 (4)
N1—C8	1.379 (4)	C5—C10	1.497 (4)
N1—H1N	0.93 (3)	C6—C7	1.368 (4)
C1—C2	1.374 (3)	C6—H6	0.9300
C1—H1	0.9300	C7—C8	1.385 (4)
C2—C9	1.421 (3)	C7—H7	0.9300
C2—C3	1.444 (3)	C9—H9	0.9300
C3—C4	1.397 (3)	C10—H10A	0.9600
C3—C8	1.408 (3)	C10—H10B	0.9600
C4—C5	1.377 (3)	C10—H10C	0.9600

C1—N1—C8	109.7 (2)	C7—C6—C5	122.3 (3)
C1—N1—H1N	121.9 (18)	C7—C6—H6	118.8
C8—N1—H1N	128.1 (18)	C5—C6—H6	118.8
N1—C1—C2	111.0 (3)	C6—C7—C8	118.1 (2)
N1—C1—H1	124.5	C6—C7—H7	121.0
C2—C1—H1	124.5	C8—C7—H7	121.0
C1—C2—C9	124.3 (3)	N1—C8—C7	131.4 (2)
C1—C2—C3	105.7 (2)	N1—C8—C3	107.3 (2)
C9—C2—C3	130.0 (2)	C7—C8—C3	121.2 (3)
C4—C3—C8	119.0 (2)	O1—C9—C2	125.6 (3)
C4—C3—C2	134.7 (2)	O1—C9—H9	117.2
C8—C3—C2	106.3 (2)	C2—C9—H9	117.2
C5—C4—C3	120.0 (2)	C5—C10—H10A	109.5
C5—C4—H4	120.0	C5—C10—H10B	109.5
C3—C4—H4	120.0	H10A—C10—H10B	109.5
C4—C5—C6	119.4 (3)	C5—C10—H10C	109.5
C4—C5—C10	119.9 (2)	H10A—C10—H10C	109.5
C6—C5—C10	120.7 (3)	H10B—C10—H10C	109.5

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N1/C1/C2/C3/C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.93 (3)	1.90 (3)	2.818 (3)	169 (3)
C9—H9···Cgⁱⁱ	0.93	2.91	3.312 (3)	107

Symmetry codes: (i) −x+1/2, y−1, z−1/2; (ii) −x+1/2, y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₉NO
M_r	159.18
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	296
a, b, c (Å)	16.9456 (19), 5.7029 (6), 8.6333 (9)
V (Å³)	834.31 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.47 × 0.15 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.962, 0.996
No. of measured, independent and observed [I > 2σ(I)] reflections	5499, 1147, 717
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.677

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.107, 0.98
No. of reflections	1147
No. of parameters	113
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.14

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), X-SEED (Barbour, 2001), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the N1/C1/C2/C3/C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.93 (3)	1.90 (3)	2.818 (3)	169 (3)
C9—H9···Cgⁱⁱ	0.93	2.91	3.312 (3)	107

Symmetry codes: (i) −x+1/2, y−1, z−1/2; (ii) −x+1/2, y, z+1/2.

Acknowledgements

We thank the University of Malaya for funding this study (UMRG grant No. RG 066/12BIO).

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Johnson, J. E., Canseco, D. C., Dolliver, D. D., Schetz, J. A. & Fronczek, F. R. (2009). J. Chem. Crystallogr. 39, 329–336. Web of Science CSD CrossRef CAS Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2691

doi:10.1107/S1600536812034873

Open

access