2-Chloro-6-methoxy­quinoline-3-carbaldehyde

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

doi:10.1107/S1600536809040847

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2723

https://doi.org/10.1107/S1600536809040847

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2-Chloro-6-methoxyquinoline-3-carbaldehyde

R. Subashini,^a F. Nawaz Khan,^a Machhindra Gund,^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 13 October 2009)

The quinoline fused-ring system of the title compound, C₁₁H₈ClNO₂, is planar (r.m.s. deviation = 0.0095 Å); the formyl group is slightly bent out of this plane [C—C—C—O torsion angles = −2.4 (3) and 175.9 (2)°].

Related literature

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

Experimental

Crystal data

C₁₁H₈ClNO₂
M_r = 221.63
Monoclinic, P 2₁ /c
a = 7.7072 (9) Å
b = 14.3474 (13) Å
c = 9.3487 (10) Å
β = 109.415 (2)°
V = 974.98 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.37 mm⁻¹
T = 290 K
0.24 × 0.21 × 0.18 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.917, T_max = 0.937
6533 measured reflections
2221 independent reflections
1702 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.115
S = 1.03
2221 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809040847/bt5087sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040847/bt5087Isup2.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-anisyl)acetamide (1.65 g, 10 mmol). The mixture was heated at 353 K for 15 h. The mixture was poured onto ice; 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: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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. Anisotropic displacement ellipsoid plot (Barbour, 2001) of the title compound at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-Chloro-6-methoxyquinoline-3-carbaldehyde top

Crystal data top

C₁₁H₈ClNO₂	F(000) = 456
M_r = 221.63	D_x = 1.510 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 842 reflections
a = 7.7072 (9) Å	θ = 2.0–24.7°
b = 14.3474 (13) Å	µ = 0.37 mm⁻¹
c = 9.3487 (10) Å	T = 290 K
β = 109.415 (2)°	Block, colorless
V = 974.98 (18) Å³	0.24 × 0.21 × 0.18 mm
Z = 4

Data collection top

Bruker SMART area-detector diffractometer	2221 independent reflections
Radiation source: fine-focus sealed tube	1702 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 27.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→9
T_min = 0.917, T_max = 0.937	k = −18→10
6533 measured reflections	l = −12→12

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) = 0.115	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.068P)² + 0.0419P] where P = (F_o² + 2F_c²)/3
2221 reflections	(Δ/σ)_max = 0.001
137 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₁₁H₈ClNO₂	V = 974.98 (18) Å³
M_r = 221.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.7072 (9) Å	µ = 0.37 mm⁻¹
b = 14.3474 (13) Å	T = 290 K
c = 9.3487 (10) Å	0.24 × 0.21 × 0.18 mm
β = 109.415 (2)°

Data collection top

Bruker SMART area-detector diffractometer	2221 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1702 reflections with I > 2σ(I)
T_min = 0.917, T_max = 0.937	R_int = 0.030
6533 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
2221 reflections	Δρ_min = −0.24 e Å⁻³
137 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.12213 (7)	0.04921 (3)	0.68956 (6)	0.05816 (19)
O1	0.02629 (18)	0.34429 (9)	0.71932 (16)	0.0563 (4)
O2	0.77125 (17)	0.34949 (8)	0.35759 (14)	0.0480 (3)
N1	0.35512 (19)	0.10458 (9)	0.56310 (15)	0.0399 (3)
C1	0.2333 (2)	0.13533 (11)	0.62026 (18)	0.0386 (4)
C2	0.1913 (2)	0.23022 (11)	0.63341 (17)	0.0365 (4)
C3	0.2892 (2)	0.29435 (11)	0.58240 (18)	0.0366 (3)
H3	0.2659	0.3576	0.5885	0.044*
C4	0.4244 (2)	0.26584 (10)	0.52104 (16)	0.0340 (3)
C5	0.5323 (2)	0.32923 (11)	0.47029 (18)	0.0372 (4)
H5	0.5165	0.3931	0.4772	0.045*
C6	0.6601 (2)	0.29554 (11)	0.41088 (18)	0.0375 (4)
C7	0.6864 (2)	0.19874 (12)	0.40126 (18)	0.0406 (4)
H7	0.7733	0.1771	0.3600	0.049*
C8	0.5865 (2)	0.13662 (11)	0.45142 (18)	0.0403 (4)
H8	0.6067	0.0730	0.4456	0.048*
C9	0.4520 (2)	0.16836 (10)	0.51239 (17)	0.0342 (3)
C10	0.0534 (2)	0.26334 (14)	0.70166 (19)	0.0446 (4)
H10	−0.0153	0.2191	0.7322	0.054*
C11	0.7544 (3)	0.44805 (12)	0.3677 (2)	0.0542 (5)
H11A	0.8378	0.4783	0.3259	0.081*
H11B	0.7835	0.4657	0.4721	0.081*
H11C	0.6306	0.4665	0.3120	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0724 (4)	0.0424 (3)	0.0754 (4)	−0.0099 (2)	0.0455 (3)	0.0028 (2)
O1	0.0572 (8)	0.0491 (9)	0.0728 (9)	0.0069 (6)	0.0355 (7)	−0.0077 (6)
O2	0.0529 (7)	0.0395 (7)	0.0631 (8)	−0.0047 (5)	0.0347 (6)	−0.0021 (5)
N1	0.0497 (8)	0.0302 (8)	0.0442 (7)	0.0003 (6)	0.0216 (6)	−0.0002 (5)
C1	0.0455 (9)	0.0337 (8)	0.0394 (8)	−0.0033 (7)	0.0176 (7)	0.0014 (6)
C2	0.0376 (8)	0.0358 (8)	0.0369 (8)	0.0018 (6)	0.0136 (7)	−0.0017 (6)
C3	0.0423 (8)	0.0285 (8)	0.0411 (8)	0.0043 (6)	0.0168 (7)	−0.0013 (6)
C4	0.0379 (8)	0.0307 (8)	0.0346 (8)	0.0030 (6)	0.0135 (6)	0.0001 (6)
C5	0.0425 (8)	0.0278 (8)	0.0435 (8)	0.0003 (6)	0.0174 (7)	−0.0018 (6)
C6	0.0393 (8)	0.0353 (9)	0.0397 (8)	−0.0029 (6)	0.0157 (7)	−0.0001 (6)
C7	0.0437 (9)	0.0385 (9)	0.0442 (9)	0.0056 (7)	0.0209 (7)	−0.0032 (7)
C8	0.0493 (9)	0.0303 (9)	0.0448 (9)	0.0069 (7)	0.0205 (7)	−0.0013 (6)
C9	0.0406 (8)	0.0278 (8)	0.0350 (8)	0.0019 (6)	0.0138 (6)	−0.0001 (6)
C10	0.0431 (9)	0.0510 (11)	0.0445 (9)	0.0002 (8)	0.0208 (7)	−0.0024 (8)
C11	0.0605 (12)	0.0381 (10)	0.0751 (13)	−0.0109 (8)	0.0373 (10)	−0.0039 (8)

Geometric parameters (Å, º) top

Cl1—C1	1.7461 (16)	C4—C9	1.421 (2)
O1—C10	1.201 (2)	C5—C6	1.370 (2)
O2—C6	1.3654 (18)	C5—H5	0.9300
O2—C11	1.426 (2)	C6—C7	1.411 (2)
N1—C1	1.302 (2)	C7—C8	1.359 (2)
N1—C9	1.362 (2)	C7—H7	0.9300
C1—C2	1.414 (2)	C8—C9	1.414 (2)
C2—C3	1.372 (2)	C8—H8	0.9300
C2—C10	1.487 (2)	C10—H10	0.9300
C3—C4	1.407 (2)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.416 (2)	C11—H11C	0.9600

C6—O2—C11	117.12 (13)	C5—C6—C7	120.73 (14)
C1—N1—C9	117.96 (13)	C8—C7—C6	120.92 (14)
N1—C1—C2	125.38 (14)	C8—C7—H7	119.5
N1—C1—Cl1	114.97 (12)	C6—C7—H7	119.5
C2—C1—Cl1	119.62 (12)	C7—C8—C9	120.21 (14)
C3—C2—C1	116.56 (14)	C7—C8—H8	119.9
C3—C2—C10	119.25 (15)	C9—C8—H8	119.9
C1—C2—C10	124.17 (15)	N1—C9—C8	118.96 (14)
C2—C3—C4	120.94 (14)	N1—C9—C4	122.11 (13)
C2—C3—H3	119.5	C8—C9—C4	118.93 (14)
C4—C3—H3	119.5	O1—C10—C2	123.35 (17)
C3—C4—C5	123.14 (14)	O1—C10—H10	118.3
C3—C4—C9	117.05 (14)	C2—C10—H10	118.3
C5—C4—C9	119.81 (13)	O2—C11—H11A	109.5
C6—C5—C4	119.40 (15)	O2—C11—H11B	109.5
C6—C5—H5	120.3	H11A—C11—H11B	109.5
C4—C5—H5	120.3	O2—C11—H11C	109.5
O2—C6—C5	124.81 (15)	H11A—C11—H11C	109.5
O2—C6—C7	114.46 (13)	H11B—C11—H11C	109.5

C9—N1—C1—C2	0.5 (2)	C4—C5—C6—C7	−0.6 (2)
C9—N1—C1—Cl1	−177.49 (11)	O2—C6—C7—C8	179.38 (15)
N1—C1—C2—C3	−0.6 (2)	C5—C6—C7—C8	−0.4 (2)
Cl1—C1—C2—C3	177.35 (12)	C6—C7—C8—C9	0.9 (2)
N1—C1—C2—C10	−178.93 (16)	C1—N1—C9—C8	179.30 (15)
Cl1—C1—C2—C10	−1.0 (2)	C1—N1—C9—C4	0.3 (2)
C1—C2—C3—C4	−0.2 (2)	C7—C8—C9—N1	−179.39 (15)
C10—C2—C3—C4	178.22 (15)	C7—C8—C9—C4	−0.4 (2)
C2—C3—C4—C5	−178.40 (15)	C3—C4—C9—N1	−1.1 (2)
C2—C3—C4—C9	1.0 (2)	C5—C4—C9—N1	178.34 (14)
C3—C4—C5—C6	−179.51 (15)	C3—C4—C9—C8	179.98 (14)
C9—C4—C5—C6	1.1 (2)	C5—C4—C9—C8	−0.6 (2)
C11—O2—C6—C5	1.3 (2)	C3—C2—C10—O1	−2.4 (3)
C11—O2—C6—C7	−178.48 (16)	C1—C2—C10—O1	175.9 (2)
C4—C5—C6—O2	179.62 (15)

Experimental details

Crystal data
Chemical formula	C₁₁H₈ClNO₂
M_r	221.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	7.7072 (9), 14.3474 (13), 9.3487 (10)
β (°)	109.415 (2)
V (Å³)	974.98 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.24 × 0.21 × 0.18

Data collection
Diffractometer	Bruker SMART area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.917, 0.937
No. of measured, independent and observed [I > 2σ(I)] reflections	6533, 2221, 1702
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.115, 1.03
No. of reflections	2221
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.24

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), 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 also thank VIT University and the University of Malaya for supporting this study.

References

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Meth-Cohn, O. (1993). Heterocycles, 35, 539–557. CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. 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