2-Chloro­quinoline-3-carbaldehyde

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

doi:10.1107/S1600536809040665

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2710

https://doi.org/10.1107/S1600536809040665

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2-Chloroquinoline-3-carbaldehyde

F. Nawaz Khan,^a R. Subashini,^a Rajesh Kumar,^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 system of the title compound, C₁₀H₆ClNO, is planar (r.m.s. deviation = 0.018 Å); the formyl group is slightly bent out of the plane of the fused ring system [C—C—C—O torsion angle = 8.2 (3)°].

Related literature

For the synthesis of 2-chloroquinoline-3-carbaldehyde by Vilsmeier–Haack cyclization, see: Ali et al. (2001 , 2002 ); Mogilaiah et al. (2002 ); Pawar et al. (1990 ); Srivastava & Singh (2005 ). For a review of the synthesis of quinolines by this reaction, see: Meth-Cohn (1993 ).

Experimental

Crystal data

C₁₀H₆ClNO
M_r = 191.61
Monoclinic, P 2₁ /n
a = 11.8784 (9) Å
b = 3.9235 (3) Å
c = 18.1375 (12) Å
β = 101.365 (4)°
V = 828.72 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 290 K
0.24 × 0.18 × 0.14 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.908, T_max = 0.945
6886 measured reflections
1889 independent reflections
1626 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.145
S = 1.19
1889 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.29 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/S1600536809040665/tk2549sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040665/tk2549Isup2.hkl

checkCIF report

Related literature top

For the synthesis of 2-chloroquinoline-3-carbaldehyde by Vilsmeier–Haack cyclization, see: Ali et al. (2001, 2002); Mogilaiah et al. (2002); Pawar et al. (1990); Srivastava & Singh (2005). For a review of the synthesis of quinolines by this 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-phenylacetamide (1.35 g, 10 mmol), 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 the synthesis of 2-chloroquinoline-3-carbaldehyde by Vilsmeier–Haack cyclization, see: Ali et al. (2001, 2002); Mogilaiah et al. (2002); Pawar et al. (1990); Srivastava & Singh (2005). For a review of the synthesis of quinolines by this 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. Thermal ellipsoid plot (Barbour, 2001) of C₁₀H₆ClNO at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-Chloroquinoline-3-carbaldehyde top

Crystal data top

C₁₀H₆ClNO	F(000) = 392
M_r = 191.61	D_x = 1.536 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 781 reflections
a = 11.8784 (9) Å	θ = 2.1–24.3°
b = 3.9235 (3) Å	µ = 0.41 mm⁻¹
c = 18.1375 (12) Å	T = 290 K
β = 101.365 (4)°	Block, colorless
V = 828.72 (10) Å³	0.24 × 0.18 × 0.14 mm
Z = 4

Data collection top

Bruker SMART area-detector diffractometer	1889 independent reflections
Radiation source: fine-focus sealed tube	1626 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
φ and ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.908, T_max = 0.945	k = −3→5
6886 measured reflections	l = −23→23

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.0923P)² + 0.077P] where P = (F_o² + 2F_c²)/3
1889 reflections	(Δ/σ)_max = 0.001
118 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₀H₆ClNO	V = 828.72 (10) Å³
M_r = 191.61	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.8784 (9) Å	µ = 0.41 mm⁻¹
b = 3.9235 (3) Å	T = 290 K
c = 18.1375 (12) Å	0.24 × 0.18 × 0.14 mm
β = 101.365 (4)°

Data collection top

Bruker SMART area-detector diffractometer	1889 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1626 reflections with I > 2σ(I)
T_min = 0.908, T_max = 0.945	R_int = 0.021
6886 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.19	Δρ_max = 0.36 e Å⁻³
1889 reflections	Δρ_min = −0.29 e Å⁻³
118 parameters

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

	x	y	z	U_iso*/U_eq
Cl1	0.24556 (4)	0.22180 (12)	0.67041 (2)	0.0464 (2)
O1	0.51095 (11)	0.8482 (4)	0.61287 (8)	0.0550 (4)
N1	0.15508 (12)	0.2731 (3)	0.52950 (9)	0.0353 (3)
C1	0.24476 (14)	0.3582 (4)	0.57833 (9)	0.0319 (4)
C2	0.34039 (13)	0.5468 (4)	0.56384 (9)	0.0323 (4)
C3	0.33695 (13)	0.6369 (4)	0.49061 (9)	0.0334 (4)
H3	0.3977	0.7585	0.4781	0.040*
C4	0.24263 (13)	0.5477 (4)	0.43407 (9)	0.0324 (4)
C5	0.23434 (16)	0.6341 (5)	0.35765 (10)	0.0419 (4)
H5	0.2944	0.7483	0.3424	0.050*
C6	0.13859 (17)	0.5504 (5)	0.30635 (10)	0.0481 (5)
H6	0.1334	0.6077	0.2560	0.058*
C7	0.04727 (17)	0.3774 (6)	0.32911 (11)	0.0493 (5)
H7	−0.0180	0.3243	0.2935	0.059*
C8	0.05247 (16)	0.2861 (5)	0.40222 (12)	0.0436 (4)
H8	−0.0082	0.1699	0.4162	0.052*
C9	0.15087 (13)	0.3697 (4)	0.45629 (9)	0.0325 (4)
C10	0.43810 (15)	0.6537 (5)	0.62315 (10)	0.0407 (4)
H10	0.4432	0.5645	0.6712	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0587 (3)	0.0522 (3)	0.0308 (3)	−0.00331 (19)	0.0147 (2)	0.00444 (16)
O1	0.0435 (8)	0.0681 (10)	0.0499 (8)	−0.0161 (6)	0.0004 (6)	0.0003 (7)
N1	0.0363 (7)	0.0355 (7)	0.0355 (8)	−0.0016 (5)	0.0107 (6)	−0.0029 (5)
C1	0.0381 (8)	0.0310 (8)	0.0283 (7)	0.0020 (6)	0.0107 (6)	0.0004 (6)
C2	0.0335 (8)	0.0312 (8)	0.0321 (8)	0.0024 (6)	0.0062 (6)	−0.0007 (6)
C3	0.0329 (8)	0.0332 (8)	0.0349 (8)	−0.0001 (6)	0.0089 (6)	0.0018 (7)
C4	0.0362 (8)	0.0317 (8)	0.0299 (8)	0.0056 (6)	0.0077 (6)	−0.0005 (6)
C5	0.0489 (10)	0.0444 (9)	0.0332 (9)	0.0076 (8)	0.0101 (7)	0.0039 (7)
C6	0.0591 (11)	0.0544 (11)	0.0289 (8)	0.0166 (9)	0.0039 (8)	−0.0021 (8)
C7	0.0454 (10)	0.0560 (11)	0.0407 (10)	0.0110 (8)	−0.0058 (8)	−0.0141 (9)
C8	0.0356 (9)	0.0467 (10)	0.0466 (11)	0.0012 (7)	0.0037 (8)	−0.0120 (8)
C9	0.0331 (8)	0.0320 (8)	0.0329 (8)	0.0032 (6)	0.0072 (6)	−0.0052 (6)
C10	0.0414 (9)	0.0459 (10)	0.0332 (9)	−0.0003 (7)	0.0031 (7)	0.0017 (7)

Geometric parameters (Å, º) top

Cl1—C1	1.7519 (16)	C4—C9	1.418 (2)
O1—C10	1.196 (2)	C5—C6	1.360 (3)
N1—C1	1.288 (2)	C5—H5	0.9300
N1—C9	1.372 (2)	C6—C7	1.409 (3)
C1—C2	1.423 (2)	C6—H6	0.9300
C2—C3	1.367 (2)	C7—C8	1.363 (3)
C2—C10	1.479 (2)	C7—H7	0.9300
C3—C4	1.406 (2)	C8—C9	1.409 (2)
C3—H3	0.9300	C8—H8	0.9300
C4—C5	1.411 (2)	C10—H10	0.9300

C1—N1—C9	117.48 (14)	C5—C6—C7	120.28 (17)
N1—C1—C2	126.15 (15)	C5—C6—H6	119.9
N1—C1—Cl1	115.14 (12)	C7—C6—H6	119.9
C2—C1—Cl1	118.71 (12)	C8—C7—C6	121.46 (17)
C3—C2—C1	116.22 (14)	C8—C7—H7	119.3
C3—C2—C10	120.14 (15)	C6—C7—H7	119.3
C1—C2—C10	123.62 (15)	C7—C8—C9	119.23 (18)
C2—C3—C4	120.74 (14)	C7—C8—H8	120.4
C2—C3—H3	119.6	C9—C8—H8	120.4
C4—C3—H3	119.6	N1—C9—C8	118.45 (15)
C3—C4—C5	123.22 (15)	N1—C9—C4	121.83 (14)
C3—C4—C9	117.52 (14)	C8—C9—C4	119.71 (16)
C5—C4—C9	119.24 (15)	O1—C10—C2	123.76 (16)
C6—C5—C4	120.07 (17)	O1—C10—H10	118.1
C6—C5—H5	120.0	C2—C10—H10	118.1
C4—C5—H5	120.0

C9—N1—C1—C2	0.6 (2)	C5—C6—C7—C8	−0.8 (3)
C9—N1—C1—Cl1	−179.13 (11)	C6—C7—C8—C9	0.7 (3)
N1—C1—C2—C3	−1.8 (2)	C1—N1—C9—C8	−178.61 (14)
Cl1—C1—C2—C3	177.90 (11)	C1—N1—C9—C4	1.8 (2)
N1—C1—C2—C10	176.39 (16)	C7—C8—C9—N1	−179.43 (15)
Cl1—C1—C2—C10	−3.9 (2)	C7—C8—C9—C4	0.1 (3)
C1—C2—C3—C4	0.6 (2)	C3—C4—C9—N1	−2.9 (2)
C10—C2—C3—C4	−177.67 (14)	C5—C4—C9—N1	178.69 (15)
C2—C3—C4—C5	179.92 (15)	C3—C4—C9—C8	177.57 (15)
C2—C3—C4—C9	1.5 (2)	C5—C4—C9—C8	−0.9 (2)
C3—C4—C5—C6	−177.55 (16)	C3—C2—C10—O1	8.2 (3)
C9—C4—C5—C6	0.8 (3)	C1—C2—C10—O1	−170.0 (2)
C4—C5—C6—C7	0.0 (3)

Experimental details

Crystal data
Chemical formula	C₁₀H₆ClNO
M_r	191.61
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	290
a, b, c (Å)	11.8784 (9), 3.9235 (3), 18.1375 (12)
β (°)	101.365 (4)
V (Å³)	828.72 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.41
Crystal size (mm)	0.24 × 0.18 × 0.14

Data collection
Diffractometer	Bruker SMART area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.908, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	6886, 1889, 1626
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.145, 1.19
No. of reflections	1889
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.29

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 thank VIT University and the University of Malaya for supporting this study.

References

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