2-Chloro-8-methyl­quinoline-3-carbaldehyde

Khan, F.N.; Subashini, R.; Kushwaha, A.K.; Hathwar, V.R.; Ng, S.W.

doi:10.1107/S1600536809040859

organic compounds

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Volume 65| Part 11| November 2009| Page o2722

https://doi.org/10.1107/S1600536809040859

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2-Chloro-8-methylquinoline-3-carbaldehyde

F. Nawaz Khan,^a R. Subashini,^a Atul Kumar Kushwaha,^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, C₁₁H₈ClNO, is planar (r.m.s. deviation = 0.005 Å); the formyl group is slightly bent out of the plane [C—C—C–O1 torsion angles = 8.8 (7) and −172.8 (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
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.8576 (5) Å
b = 7.4936 (6) Å
c = 18.5003 (14) Å
V = 950.70 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 290 K
0.26 × 0.22 × 0.17 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.912, T_max = 0.941
8224 measured reflections
2174 independent reflections
1734 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.136
S = 1.00
2174 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.33 e Å⁻³
Absolute structure: Flack (1983 ), 838 Friedel pairs
Flack parameter: 0.2 (2)

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/S1600536809040859/bt5085sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040859/bt5085Isup2.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

The Vilsmeier-Haack reagent prepared from phosphorus oxytrichloride (6.5 ml, 70 mmol) and N,N-dimethylformamide (2.3 ml, 30 mmol) at 273 K was added N-(2-tolyl)acetamide (1.49 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. Thermal ellipsoid plot (Barbour, 2001) of C₁₁H₈ClNO at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-Chloro-8-methylquinoline-3-carbaldehyde top

Crystal data top

C₁₁H₈ClNO	F(000) = 424
M_r = 205.63	D_x = 1.437 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 867 reflections
a = 6.8576 (5) Å	θ = 2.0–24.4°
b = 7.4936 (6) Å	µ = 0.36 mm⁻¹
c = 18.5003 (14) Å	T = 290 K
V = 950.70 (13) Å³	Block, colorless
Z = 4	0.26 × 0.22 × 0.17 mm

Data collection top

Bruker SMART area-detector diffractometer	2174 independent reflections
Radiation source: fine-focus sealed tube	1734 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
φ and ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.912, T_max = 0.941	k = −9→9
8224 measured reflections	l = −22→24

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)] = 0.048	H-atom parameters constrained
wR(F²) = 0.136	w = 1/[σ²(F_o²) + (0.0861P)² + 0.0263P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
2174 reflections	Δρ_max = 0.25 e Å⁻³
129 parameters	Δρ_min = −0.33 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 838 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.2 (2)

Crystal data top

C₁₁H₈ClNO	V = 950.70 (13) Å³
M_r = 205.63	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.8576 (5) Å	µ = 0.36 mm⁻¹
b = 7.4936 (6) Å	T = 290 K
c = 18.5003 (14) Å	0.26 × 0.22 × 0.17 mm

Data collection top

Bruker SMART area-detector diffractometer	2174 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1734 reflections with I > 2σ(I)
T_min = 0.912, T_max = 0.941	R_int = 0.043
8224 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.136	Δρ_max = 0.25 e Å⁻³
S = 1.00	Δρ_min = −0.33 e Å⁻³
2174 reflections	Absolute structure: Flack (1983), 838 Friedel pairs
129 parameters	Absolute structure parameter: 0.2 (2)
0 restraints

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

	x	y	z	U_iso*/U_eq
Cl1	0.87010 (13)	1.14505 (9)	0.37890 (4)	0.0579 (3)
O1	0.8672 (5)	0.6106 (3)	0.29577 (10)	0.0763 (6)
N1	0.8717 (4)	0.9871 (2)	0.50346 (10)	0.0366 (4)
C1	0.8734 (5)	0.9563 (3)	0.43459 (13)	0.0368 (5)
C2	0.8754 (5)	0.7858 (3)	0.40176 (11)	0.0398 (5)
C3	0.8734 (5)	0.6423 (4)	0.44734 (12)	0.0389 (5)
H3	0.8741	0.5276	0.4281	0.047*
C4	0.8705 (4)	0.6651 (3)	0.52293 (10)	0.0344 (5)
C5	0.8691 (5)	0.5212 (3)	0.57186 (14)	0.0443 (6)
H5	0.8707	0.4045	0.5547	0.053*
C6	0.8654 (6)	0.5531 (3)	0.64410 (13)	0.0468 (6)
H6	0.8633	0.4585	0.6766	0.056*
C7	0.8648 (5)	0.7301 (4)	0.66955 (13)	0.0443 (6)
H7	0.8614	0.7491	0.7192	0.053*
C8	0.8690 (4)	0.8754 (3)	0.62492 (11)	0.0372 (5)
C9	0.8702 (4)	0.8426 (3)	0.54918 (11)	0.0327 (4)
C10	0.8840 (6)	0.7545 (5)	0.32246 (14)	0.0551 (7)
H10	0.9034	0.8521	0.2922	0.066*
C11	0.8698 (7)	1.0624 (3)	0.65349 (14)	0.0547 (7)
H11A	0.8779	1.0598	0.7053	0.082*
H11B	0.7519	1.1218	0.6392	0.082*
H11C	0.9801	1.1255	0.6343	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0687 (4)	0.0591 (4)	0.0459 (4)	0.0008 (5)	0.0006 (4)	0.0218 (3)
O1	0.0887 (16)	0.1007 (17)	0.0394 (10)	−0.008 (2)	−0.0031 (13)	−0.0254 (11)
N1	0.0371 (10)	0.0403 (10)	0.0324 (10)	−0.0007 (12)	0.0005 (12)	0.0028 (7)
C1	0.0327 (11)	0.0459 (13)	0.0318 (12)	0.0001 (17)	−0.0007 (16)	0.0062 (10)
C2	0.0347 (11)	0.0576 (14)	0.0272 (10)	−0.0003 (15)	−0.0008 (12)	−0.0019 (10)
C3	0.0393 (11)	0.0427 (11)	0.0348 (12)	−0.002 (2)	−0.0005 (14)	−0.0084 (10)
C4	0.0323 (10)	0.0410 (11)	0.0300 (10)	−0.0007 (15)	0.0005 (11)	−0.0004 (8)
C5	0.0509 (14)	0.0398 (12)	0.0422 (14)	0.0026 (19)	0.0008 (19)	0.0040 (10)
C6	0.0509 (14)	0.0519 (14)	0.0375 (12)	0.0021 (17)	0.0007 (16)	0.0120 (10)
C7	0.0457 (14)	0.0596 (15)	0.0276 (11)	0.0043 (19)	−0.0022 (15)	0.0020 (11)
C8	0.0344 (10)	0.0461 (12)	0.0310 (11)	0.0029 (12)	−0.0009 (13)	−0.0014 (9)
C9	0.0292 (10)	0.0407 (11)	0.0280 (10)	−0.0001 (16)	0.0004 (12)	0.0002 (9)
C10	0.0538 (17)	0.084 (2)	0.0278 (12)	0.000 (2)	−0.0010 (17)	−0.0032 (13)
C11	0.0716 (17)	0.0543 (15)	0.0384 (13)	0.003 (2)	−0.0005 (19)	−0.0128 (11)

Geometric parameters (Å, º) top

Cl1—C1	1.750 (2)	C5—H5	0.9300
O1—C10	1.191 (4)	C6—C7	1.407 (4)
N1—C1	1.295 (3)	C6—H6	0.9300
N1—C9	1.374 (3)	C7—C8	1.367 (3)
C1—C2	1.415 (3)	C7—H7	0.9300
C2—C3	1.367 (3)	C8—C9	1.423 (3)
C2—C10	1.487 (3)	C8—C11	1.498 (3)
C3—C4	1.409 (3)	C10—H10	0.9300
C3—H3	0.9300	C11—H11A	0.9600
C4—C5	1.408 (3)	C11—H11B	0.9600
C4—C9	1.416 (3)	C11—H11C	0.9600
C5—C6	1.358 (4)

C1—N1—C9	117.73 (18)	C8—C7—C6	123.3 (2)
N1—C1—C2	125.68 (19)	C8—C7—H7	118.4
N1—C1—Cl1	115.80 (18)	C6—C7—H7	118.4
C2—C1—Cl1	118.52 (18)	C7—C8—C9	117.2 (2)
C3—C2—C1	116.47 (19)	C7—C8—C11	122.2 (2)
C3—C2—C10	119.0 (2)	C9—C8—C11	120.6 (2)
C1—C2—C10	124.5 (2)	N1—C9—C4	121.95 (19)
C2—C3—C4	121.1 (2)	N1—C9—C8	118.06 (19)
C2—C3—H3	119.4	C4—C9—C8	119.99 (19)
C4—C3—H3	119.4	O1—C10—C2	123.2 (3)
C5—C4—C3	123.0 (2)	O1—C10—H10	118.4
C5—C4—C9	119.9 (2)	C2—C10—H10	118.4
C3—C4—C9	117.0 (2)	C8—C11—H11A	109.5
C6—C5—C4	119.9 (2)	C8—C11—H11B	109.5
C6—C5—H5	120.1	H11A—C11—H11B	109.5
C4—C5—H5	120.1	C8—C11—H11C	109.5
C5—C6—C7	119.7 (2)	H11A—C11—H11C	109.5
C5—C6—H6	120.2	H11B—C11—H11C	109.5
C7—C6—H6	120.2

C9—N1—C1—C2	−0.5 (5)	C6—C7—C8—C9	1.3 (5)
C9—N1—C1—Cl1	178.7 (2)	C6—C7—C8—C11	−179.5 (4)
N1—C1—C2—C3	0.6 (5)	C1—N1—C9—C4	0.0 (4)
Cl1—C1—C2—C3	−178.6 (3)	C1—N1—C9—C8	179.8 (3)
N1—C1—C2—C10	−177.9 (3)	C5—C4—C9—N1	179.9 (3)
Cl1—C1—C2—C10	2.9 (5)	C3—C4—C9—N1	0.3 (5)
C1—C2—C3—C4	−0.3 (5)	C5—C4—C9—C8	0.2 (4)
C10—C2—C3—C4	178.3 (3)	C3—C4—C9—C8	−179.4 (2)
C2—C3—C4—C5	−179.8 (3)	C7—C8—C9—N1	179.1 (3)
C2—C3—C4—C9	−0.1 (5)	C11—C8—C9—N1	−0.1 (5)
C3—C4—C5—C6	−179.7 (4)	C7—C8—C9—C4	−1.1 (4)
C9—C4—C5—C6	0.7 (5)	C11—C8—C9—C4	179.6 (3)
C4—C5—C6—C7	−0.6 (6)	C3—C2—C10—O1	8.8 (7)
C5—C6—C7—C8	−0.4 (6)	C1—C2—C10—O1	−172.8 (4)

Experimental details

Crystal data
Chemical formula	C₁₁H₈ClNO
M_r	205.63
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	290
a, b, c (Å)	6.8576 (5), 7.4936 (6), 18.5003 (14)
V (Å³)	950.70 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.26 × 0.22 × 0.17

Data collection
Diffractometer	Bruker SMART area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.912, 0.941
No. of measured, independent and observed [I > 2σ(I)] reflections	8224, 2174, 1734
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.136, 1.00
No. of reflections	2174
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.33
Absolute structure	Flack (1983), 838 Friedel pairs
Absolute structure parameter	0.2 (2)

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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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
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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. (2009). publCIF. In preparation. Google Scholar