2-Chloro-7,8-dimethyl­quinoline-3-carbaldehyde

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

doi:10.1107/S1600536809040860

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2709

https://doi.org/10.1107/S1600536809040860

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2-Chloro-7,8-dimethylquinoline-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 10 October 2009)

All the non-H atoms of the title compound, C₁₂H₁₀ClNO, lie on a crystallographic mirror plane orientated perpendicular to the crystallographic b axis.

Related literature

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

Experimental

Crystal data

C₁₂H₁₀ClNO
M_r = 219.66
Orthorhombic, P n m a
a = 20.4542 (13) Å
b = 6.7393 (4) Å
c = 7.5675 (4) Å
V = 1043.16 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 290 K
0.28 × 0.21 × 0.17 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.912, T_max = 0.945
7145 measured reflections
1299 independent reflections
1078 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.115
S = 1.07
1299 reflections
94 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.30 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/S1600536809040860/bt5086sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040860/bt5086Isup2.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-(2,3-dimethylphenyl)acetamide (1.63 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 C₁₂H₁₀ClNO at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-Chloro-7,8-dimethylquinoline-3-carbaldehyde top

Crystal data top

C₁₂H₁₀ClNO	F(000) = 456
M_r = 219.66	D_x = 1.399 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 753 reflections
a = 20.4542 (13) Å	θ = 2.0–24.4°
b = 6.7393 (4) Å	µ = 0.34 mm⁻¹
c = 7.5675 (4) Å	T = 290 K
V = 1043.16 (11) Å³	Block, colorless
Z = 4	0.28 × 0.21 × 0.17 mm

Data collection top

Bruker SMART area-detector diffractometer	1299 independent reflections
Radiation source: fine-focus sealed tube	1078 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −25→26
T_min = 0.912, T_max = 0.945	k = −8→4
7145 measured reflections	l = −9→9

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) = 0.115	w = 1/[σ²(F_o²) + (0.0706P)² + 0.1712P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
1299 reflections	Δρ_max = 0.29 e Å⁻³
94 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.010 (2)

Crystal data top

C₁₂H₁₀ClNO	V = 1043.16 (11) Å³
M_r = 219.66	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 20.4542 (13) Å	µ = 0.34 mm⁻¹
b = 6.7393 (4) Å	T = 290 K
c = 7.5675 (4) Å	0.28 × 0.21 × 0.17 mm

Data collection top

Bruker SMART area-detector diffractometer	1299 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1078 reflections with I > 2σ(I)
T_min = 0.912, T_max = 0.945	R_int = 0.022
7145 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.07	Δρ_max = 0.29 e Å⁻³
1299 reflections	Δρ_min = −0.30 e Å⁻³
94 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.59400 (3)	0.2500	0.07517 (7)	0.0568 (2)
N1	0.48555 (8)	0.2500	0.24995 (19)	0.0363 (4)
O1	0.68317 (9)	0.2500	0.5872 (3)	0.0672 (5)
C1	0.54815 (9)	0.2500	0.2711 (2)	0.0369 (4)
C2	0.58228 (10)	0.2500	0.4343 (3)	0.0385 (4)
C3	0.54382 (10)	0.2500	0.5832 (3)	0.0382 (4)
H3	0.5635	0.2500	0.6939	0.046*
C4	0.47569 (10)	0.2500	0.5712 (2)	0.0347 (4)
C5	0.43407 (11)	0.2500	0.7208 (3)	0.0428 (5)
H5	0.4517	0.2500	0.8341	0.051*
C6	0.36779 (11)	0.2500	0.6971 (3)	0.0461 (5)
H6	0.3408	0.2500	0.7960	0.055*
C7	0.33908 (10)	0.2500	0.5279 (3)	0.0411 (5)
C8	0.37829 (9)	0.2500	0.3777 (3)	0.0361 (4)
C9	0.44701 (9)	0.2500	0.3993 (2)	0.0322 (4)
C10	0.65428 (11)	0.2500	0.4503 (3)	0.0531 (6)
H10	0.6787	0.2500	0.3467	0.064*
C11	0.26571 (11)	0.2500	0.5126 (4)	0.0583 (6)
H11A	0.2468	0.2766	0.6262	0.087*	0.50
H11B	0.2512	0.1227	0.4713	0.087*	0.50
H11C	0.2524	0.3507	0.4305	0.087*	0.50
C12	0.34939 (11)	0.2500	0.1950 (3)	0.0532 (6)
H12A	0.3794	0.1882	0.1144	0.080*	0.50
H12B	0.3414	0.3842	0.1583	0.080*	0.50
H12C	0.3090	0.1776	0.1957	0.080*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0424 (3)	0.0881 (5)	0.0400 (3)	0.000	0.0087 (2)	0.000
N1	0.0355 (8)	0.0437 (8)	0.0298 (7)	0.000	−0.0008 (6)	0.000
O1	0.0480 (10)	0.0820 (12)	0.0716 (12)	0.000	−0.0252 (9)	0.000
C1	0.0356 (10)	0.0415 (9)	0.0336 (9)	0.000	0.0018 (7)	0.000
C2	0.0344 (10)	0.0387 (9)	0.0423 (11)	0.000	−0.0058 (7)	0.000
C3	0.0417 (11)	0.0389 (9)	0.0341 (9)	0.000	−0.0097 (7)	0.000
C4	0.0411 (10)	0.0344 (9)	0.0286 (9)	0.000	−0.0022 (7)	0.000
C5	0.0497 (12)	0.0513 (11)	0.0275 (9)	0.000	0.0003 (8)	0.000
C6	0.0483 (12)	0.0556 (11)	0.0343 (10)	0.000	0.0078 (9)	0.000
C7	0.0357 (10)	0.0453 (10)	0.0423 (10)	0.000	0.0028 (8)	0.000
C8	0.0351 (10)	0.0386 (9)	0.0346 (9)	0.000	−0.0021 (7)	0.000
C9	0.0361 (9)	0.0324 (8)	0.0281 (8)	0.000	−0.0014 (7)	0.000
C10	0.0375 (11)	0.0623 (13)	0.0595 (14)	0.000	−0.0064 (10)	0.000
C11	0.0367 (11)	0.0783 (16)	0.0600 (15)	0.000	0.0085 (10)	0.000
C12	0.0395 (11)	0.0814 (15)	0.0387 (11)	0.000	−0.0054 (9)	0.000

Geometric parameters (Å, º) top

Cl1—C1	1.7545 (19)	C6—C7	1.409 (3)
N1—C1	1.290 (2)	C6—H6	0.9300
N1—C9	1.378 (2)	C7—C8	1.391 (3)
O1—C10	1.192 (3)	C7—C11	1.505 (3)
C1—C2	1.419 (3)	C8—C9	1.415 (3)
C2—C3	1.374 (3)	C8—C12	1.504 (3)
C2—C10	1.478 (3)	C10—H10	0.9300
C3—C4	1.396 (3)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.416 (3)	C11—H11C	0.9600
C4—C9	1.427 (2)	C12—H12A	0.9600
C5—C6	1.367 (3)	C12—H12B	0.9600
C5—H5	0.9300	C12—H12C	0.9600

C1—N1—C9	117.76 (16)	C7—C8—C9	118.58 (17)
N1—C1—C2	126.61 (17)	C7—C8—C12	121.64 (18)
N1—C1—Cl1	115.19 (14)	C9—C8—C12	119.79 (17)
C2—C1—Cl1	118.20 (15)	N1—C9—C8	118.25 (15)
C3—C2—C1	115.60 (18)	N1—C9—C4	120.82 (16)
C3—C2—C10	120.21 (18)	C8—C9—C4	120.92 (16)
C1—C2—C10	124.20 (19)	O1—C10—C2	124.4 (2)
C2—C3—C4	121.19 (17)	O1—C10—H10	117.8
C2—C3—H3	119.4	C2—C10—H10	117.8
C4—C3—H3	119.4	C7—C11—H11A	109.5
C3—C4—C5	123.21 (17)	C7—C11—H11B	109.5
C3—C4—C9	118.02 (16)	H11A—C11—H11B	109.5
C5—C4—C9	118.77 (18)	C7—C11—H11C	109.5
C6—C5—C4	119.43 (18)	H11A—C11—H11C	109.5
C6—C5—H5	120.3	H11B—C11—H11C	109.5
C4—C5—H5	120.3	C8—C12—H12A	109.5
C5—C6—C7	122.15 (18)	C8—C12—H12B	109.5
C5—C6—H6	118.9	H12A—C12—H12B	109.5
C7—C6—H6	118.9	C8—C12—H12C	109.5
C8—C7—C6	120.15 (19)	H12A—C12—H12C	109.5
C8—C7—C11	120.8 (2)	H12B—C12—H12C	109.5
C6—C7—C11	119.0 (2)

C9—N1—C1—C2	0.0	C11—C7—C8—C9	180.0
C9—N1—C1—Cl1	180.0	C6—C7—C8—C12	180.0
N1—C1—C2—C3	0.0	C11—C7—C8—C12	0.0
Cl1—C1—C2—C3	180.0	C1—N1—C9—C8	180.0
N1—C1—C2—C10	180.0	C1—N1—C9—C4	0.0
Cl1—C1—C2—C10	0.0	C7—C8—C9—N1	180.0
C1—C2—C3—C4	0.0	C12—C8—C9—N1	0.0
C10—C2—C3—C4	180.0	C7—C8—C9—C4	0.0
C2—C3—C4—C5	180.0	C12—C8—C9—C4	180.0
C2—C3—C4—C9	0.0	C3—C4—C9—N1	0.0
C3—C4—C5—C6	180.0	C5—C4—C9—N1	180.0
C9—C4—C5—C6	0.0	C3—C4—C9—C8	180.0
C4—C5—C6—C7	0.0	C5—C4—C9—C8	0.0
C5—C6—C7—C8	0.0	C3—C2—C10—O1	0.0
C5—C6—C7—C11	180.0	C1—C2—C10—O1	180.0
C6—C7—C8—C9	0.0

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀ClNO
M_r	219.66
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	290
a, b, c (Å)	20.4542 (13), 6.7393 (4), 7.5675 (4)
V (Å³)	1043.16 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.28 × 0.21 × 0.17

Data collection
Diffractometer	Bruker SMART area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.912, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	7145, 1299, 1078
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.115, 1.07
No. of reflections	1299
No. of parameters	94
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.30

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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