2-Chloro-6-methyl­quinoline-3-carbaldehyde

Khan, F.N.; Subashini, R.; Roopan, S.M.; Hathwar, V.R.; Ng, S.W.

doi:10.1107/S1600536809040653

organic compounds

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Volume 65| Part 11| November 2009| Page o2686

https://doi.org/10.1107/S1600536809040653

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2-Chloro-6-methylquinoline-3-carbaldehyde

F. Nawaz Khan,^a R. Subashini,^a S. Mohana Roopan,^a Venkatesha R. Hathwar ^b and Seik Weng Ng ^c ^*

^aChemistry Division, School of Science and Humanities, VIT University, Vellore 632 014, Tamil Nadu, India, ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 6 October 2009; accepted 6 October 2009; online 10 October 2009)

The quinolinyl fused-ring of the title compound, C₁₁H₈ClNO, is almost planar (r.m.s. deviation = 0.013 Å); the formyl group is slightly bent out of the plane of the fused ring system [C—C—C—O torsion angle = 13.5 (4)°].

Related literature

For a review of the synthesis of quinolines by the Vilsmeier–Haack reaction, see: Meth-Cohn (1993 ).

Experimental

Crystal data

C₁₁H₈ClNO
M_r = 205.63
Monoclinic, P c
a = 5.944 (1) Å
b = 3.9210 (19) Å
c = 20.390 (2) Å
β = 101.377 (15)°
V = 465.9 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 290 K
0.25 × 0.15 × 0.15 mm

Data collection

Oxford Diffraction Excalibur diffractometer
Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.913, T_max = 0.947
5980 measured reflections
2052 independent reflections
1831 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.089
S = 1.00
2052 reflections
128 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 990 Friedel pairs
Flack parameter: 0.02 (6)

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809040653/tk2550sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040653/tk2550Isup2.hkl

checkCIF report

Related literature top

For a review of the synthesis of quinolines by the Vilsmeier–Haack reaction, see: Meth-Cohn (1993).

Experimental top

A Vilsmeier-Haack adduct prepared from phosphorus oxytrichloride (6.5 ml, 70 mmol) and N,N-dimethylformamide (2.3 ml, 30 mmol) at 273 K was added to N-(4-tolyl)acetamide (1.49 g, 10 mmol), and heated at 353 K for 15 h. The mixture was then poured onto ice, and the white product was collected and dried. The compound was purified by recrystallization from a petroleum ether/ethyl acetate mixture.

Structure description top

For a review of the synthesis of quinolines by the Vilsmeier–Haack reaction, see: Meth-Cohn (1993).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₁H₈ClNO at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-Chloro-6-methylquinoline-3-carbaldehyde top

Crystal data top

C₁₁H₈ClNO	F(000) = 212
M_r = 205.63	D_x = 1.466 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 1352 reflections
a = 5.944 (1) Å	θ = 2.0–20.7°
b = 3.9210 (19) Å	µ = 0.37 mm⁻¹
c = 20.390 (2) Å	T = 290 K
β = 101.377 (15)°	Block, colorless
V = 465.9 (2) Å³	0.25 × 0.15 × 0.15 mm
Z = 2

Data collection top

Oxford Diffraction Excalibur diffractometer	2052 independent reflections
Radiation source: fine-focus sealed tube	1831 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scans	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −7→7
T_min = 0.913, T_max = 0.947	k = −5→5
5980 measured reflections	l = −26→25

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0584P)²] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2052 reflections	Δρ_max = 0.19 e Å⁻³
128 parameters	Δρ_min = −0.17 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 990 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (6)

Crystal data top

C₁₁H₈ClNO	V = 465.9 (2) Å³
M_r = 205.63	Z = 2
Monoclinic, Pc	Mo Kα radiation
a = 5.944 (1) Å	µ = 0.37 mm⁻¹
b = 3.9210 (19) Å	T = 290 K
c = 20.390 (2) Å	0.25 × 0.15 × 0.15 mm
β = 101.377 (15)°

Data collection top

Oxford Diffraction Excalibur diffractometer	2052 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1831 reflections with I > 2σ(I)
T_min = 0.913, T_max = 0.947	R_int = 0.028
5980 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.089	Δρ_max = 0.19 e Å⁻³
S = 1.00	Δρ_min = −0.17 e Å⁻³
2052 reflections	Absolute structure: Flack (1983), 990 Friedel pairs
128 parameters	Absolute structure parameter: 0.02 (6)
2 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	1.00002 (8)	1.11653 (14)	0.50000 (3)	0.04862 (17)
O1	0.4626 (4)	0.5444 (6)	0.55814 (8)	0.0676 (6)
N1	0.7865 (3)	0.9885 (5)	0.37983 (9)	0.0382 (4)
C1	0.7703 (3)	0.9492 (5)	0.44201 (10)	0.0351 (5)
C2	0.5905 (3)	0.7858 (5)	0.46557 (10)	0.0340 (4)
C3	0.4137 (4)	0.6644 (5)	0.41837 (10)	0.0341 (4)
H3	0.2906	0.5561	0.4315	0.041*
C4	0.4163 (3)	0.7021 (5)	0.34984 (10)	0.0320 (4)
C5	0.2378 (4)	0.5831 (5)	0.29839 (10)	0.0366 (4)
H5	0.1096	0.4792	0.3094	0.044*
C6	0.2519 (4)	0.6196 (5)	0.23214 (10)	0.0383 (5)
C7	0.4490 (4)	0.7786 (6)	0.21674 (10)	0.0454 (5)
H7	0.4598	0.8019	0.1721	0.054*
C8	0.6212 (4)	0.8971 (6)	0.26419 (11)	0.0441 (5)
H8	0.7474	1.0015	0.2521	0.053*
C9	0.6099 (4)	0.8627 (5)	0.33289 (10)	0.0335 (4)
C10	0.5895 (4)	0.7365 (7)	0.53783 (11)	0.0470 (5)
H10	0.6930	0.8615	0.5688	0.056*
C11	0.0664 (4)	0.4932 (7)	0.17678 (10)	0.0501 (6)
H11A	−0.0398	0.3562	0.1952	0.075*
H11B	0.1332	0.3584	0.1463	0.075*
H11C	−0.0131	0.6841	0.1534	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0366 (3)	0.0578 (3)	0.0488 (3)	−0.0066 (3)	0.00193 (19)	−0.0056 (3)
O1	0.0607 (12)	0.1037 (15)	0.0375 (9)	−0.0252 (12)	0.0074 (8)	0.0170 (10)
N1	0.0348 (9)	0.0388 (8)	0.0428 (10)	−0.0031 (7)	0.0118 (7)	−0.0002 (7)
C1	0.0309 (11)	0.0349 (11)	0.0389 (11)	0.0019 (8)	0.0056 (8)	−0.0021 (8)
C2	0.0325 (11)	0.0377 (10)	0.0325 (9)	0.0060 (9)	0.0083 (8)	0.0028 (8)
C3	0.0310 (10)	0.0375 (10)	0.0354 (11)	0.0007 (8)	0.0106 (8)	0.0031 (8)
C4	0.0327 (10)	0.0302 (10)	0.0337 (10)	0.0022 (8)	0.0077 (8)	0.0012 (8)
C5	0.0346 (11)	0.0376 (11)	0.0375 (10)	−0.0002 (8)	0.0067 (8)	0.0003 (8)
C6	0.0412 (12)	0.0384 (11)	0.0348 (10)	0.0030 (9)	0.0062 (9)	−0.0016 (8)
C7	0.0575 (15)	0.0519 (12)	0.0294 (10)	0.0032 (11)	0.0148 (10)	0.0014 (9)
C8	0.0480 (13)	0.0471 (12)	0.0421 (11)	−0.0048 (10)	0.0207 (10)	0.0018 (10)
C9	0.0355 (10)	0.0326 (10)	0.0337 (10)	0.0021 (8)	0.0099 (8)	0.0003 (8)
C10	0.0412 (13)	0.0631 (14)	0.0350 (10)	−0.0026 (11)	0.0035 (9)	0.0021 (11)
C11	0.0573 (15)	0.0555 (13)	0.0346 (11)	−0.0024 (12)	0.0019 (10)	−0.0041 (10)

Geometric parameters (Å, º) top

Cl1—C1	1.748 (2)	C5—H5	0.9300
O1—C10	1.196 (3)	C6—C7	1.416 (3)
N1—C1	1.300 (2)	C6—C11	1.498 (3)
N1—C9	1.365 (3)	C7—C8	1.345 (3)
C1—C2	1.409 (3)	C7—H7	0.9300
C2—C3	1.363 (3)	C8—C9	1.422 (3)
C2—C10	1.487 (3)	C8—H8	0.9300
C3—C4	1.408 (3)	C10—H10	0.9300
C3—H3	0.9300	C11—H11A	0.9600
C4—C9	1.414 (3)	C11—H11B	0.9600
C4—C5	1.416 (3)	C11—H11C	0.9600
C5—C6	1.377 (3)

C1—N1—C9	116.50 (17)	C8—C7—C6	122.5 (2)
N1—C1—C2	126.42 (19)	C8—C7—H7	118.7
N1—C1—Cl1	114.64 (15)	C6—C7—H7	118.7
C2—C1—Cl1	118.93 (14)	C7—C8—C9	119.9 (2)
C3—C2—C1	116.68 (17)	C7—C8—H8	120.0
C3—C2—C10	120.06 (19)	C9—C8—H8	120.0
C1—C2—C10	123.25 (19)	N1—C9—C4	122.69 (17)
C2—C3—C4	120.41 (18)	N1—C9—C8	118.51 (19)
C2—C3—H3	119.8	C4—C9—C8	118.81 (19)
C4—C3—H3	119.8	O1—C10—C2	123.4 (2)
C3—C4—C9	117.27 (17)	O1—C10—H10	118.3
C3—C4—C5	123.20 (18)	C2—C10—H10	118.3
C9—C4—C5	119.53 (17)	C6—C11—H11A	109.5
C6—C5—C4	120.73 (19)	C6—C11—H11B	109.5
C6—C5—H5	119.6	H11A—C11—H11B	109.5
C4—C5—H5	119.6	C6—C11—H11C	109.5
C5—C6—C7	118.4 (2)	H11A—C11—H11C	109.5
C5—C6—C11	121.8 (2)	H11B—C11—H11C	109.5
C7—C6—C11	119.78 (19)

C9—N1—C1—C2	1.0 (3)	C5—C6—C7—C8	−0.6 (3)
C9—N1—C1—Cl1	−179.69 (15)	C11—C6—C7—C8	−180.0 (2)
N1—C1—C2—C3	−1.7 (3)	C6—C7—C8—C9	0.4 (3)
Cl1—C1—C2—C3	179.00 (15)	C1—N1—C9—C4	0.9 (3)
N1—C1—C2—C10	177.0 (2)	C1—N1—C9—C8	−179.45 (19)
Cl1—C1—C2—C10	−2.3 (3)	C3—C4—C9—N1	−2.0 (3)
C1—C2—C3—C4	0.5 (3)	C5—C4—C9—N1	178.91 (17)
C10—C2—C3—C4	−178.30 (18)	C3—C4—C9—C8	178.38 (18)
C2—C3—C4—C9	1.2 (3)	C5—C4—C9—C8	−0.7 (3)
C2—C3—C4—C5	−179.73 (19)	C7—C8—C9—N1	−179.4 (2)
C3—C4—C5—C6	−178.44 (18)	C7—C8—C9—C4	0.2 (3)
C9—C4—C5—C6	0.6 (3)	C3—C2—C10—O1	13.5 (4)
C4—C5—C6—C7	0.0 (3)	C1—C2—C10—O1	−165.1 (3)
C4—C5—C6—C11	179.4 (2)

Experimental details

Crystal data
Chemical formula	C₁₁H₈ClNO
M_r	205.63
Crystal system, space group	Monoclinic, Pc
Temperature (K)	290
a, b, c (Å)	5.944 (1), 3.9210 (19), 20.390 (2)
β (°)	101.377 (15)
V (Å³)	465.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.25 × 0.15 × 0.15

Data collection
Diffractometer	Oxford Diffraction Excalibur diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.913, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	5980, 2052, 1831
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.089, 1.00
No. of reflections	2052
No. of parameters	128
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17
Absolute structure	Flack (1983), 990 Friedel pairs
Absolute structure parameter	0.02 (6)

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

We thank the Department of Science and Technology, India, for use of the diffraction facility at IISc under the IRHPA-DST program. FNK thanks the DST for Fast Track Proposal funding. We thank VIT University and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Meth-Cohn, O. (1993). Heterocycles, 35, 539–557. CrossRef CAS Google Scholar
Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar