2-Chloro-8-methoxy­quinoline-3-carbaldehyde

Abstract

In the title compound, C₁₁H₈ClNO₂, the quinoline fused-ring system is almost planar (r.m.s. deviation = 0.020 Å). The formyl group is slightly bent out of the quinoline plane [deviation of the O atom = 0.371 (2) Å].

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,

• a = 14.4763 (8) Å

• b = 3.9246 (2) Å

• c = 17.6295 (9) Å

• β = 104.802 (3)°

• V = 968.36 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 0.37 mm⁻¹

• T = 290 K

• 0.30 × 0.18 × 0.11 mm

Data collection

• Bruker SMART area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.897, T _max = 0.961

• 8150 measured reflections

• 2212 independent reflections

• 1769 reflections with I > 2σ(I)

• R _int = 0.026

Refinement

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.149

• S = 1.18

• 2212 reflections

• 137 parameters

• H-atom parameters constrained

• Δρ_max = 0.30 e Å⁻³

• Δρ_min = −0.38 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Experimental

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 N-(2-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 to yield colourless blocks of (I).

Refinement

The H-atoms were placed in calculated positions (C–H 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U(C).

Figures

Fig. 1.

The molecular structure of (I) at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C11H8ClNO2	F(000) = 456
Mr = 221.63	Dx = 1.520 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 943 reflections
a = 14.4763 (8) Å	θ = 1.9–24.6°
b = 3.9246 (2) Å	µ = 0.37 mm−1
c = 17.6295 (9) Å	T = 290 K
β = 104.802 (3)°	Block, colourless
V = 968.36 (9) Å3	0.30 × 0.18 × 0.11 mm
Z = 4

Data collection

Bruker SMART area-detector diffractometer	2212 independent reflections
Radiation source: fine-focus sealed tube	1769 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
Tmin = 0.897, Tmax = 0.961	k = −4→5
8150 measured reflections	l = −22→22

Refinement

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149	H-atom parameters constrained
S = 1.18	w = 1/[σ2(Fo2) + (0.0883P)2 + 0.0632P] where P = (Fo2 + 2Fc2)/3
2212 reflections	(Δ/σ)max = 0.001
137 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.80902 (4)	0.23452 (14)	0.68475 (3)	0.0499 (2)
N1	0.71583 (11)	0.3286 (4)	0.54057 (8)	0.0338 (4)
O1	1.02603 (11)	0.8263 (5)	0.61921 (10)	0.0627 (5)
O2	0.54659 (9)	0.2331 (4)	0.44173 (8)	0.0450 (4)
C1	0.79779 (12)	0.3856 (5)	0.58921 (9)	0.0333 (4)
C2	0.87625 (12)	0.5588 (5)	0.57179 (10)	0.0347 (4)
C3	0.86350 (13)	0.6661 (5)	0.49563 (10)	0.0344 (4)
H3	0.9129	0.7785	0.4811	0.041*
C4	0.77669 (12)	0.6081 (5)	0.43926 (10)	0.0320 (4)
C5	0.75979 (14)	0.7149 (5)	0.36018 (11)	0.0377 (4)
H5	0.8080	0.8205	0.3426	0.045*
C6	0.67289 (14)	0.6619 (5)	0.31039 (10)	0.0395 (4)
H6	0.6620	0.7325	0.2585	0.047*
C7	0.59819 (13)	0.5015 (5)	0.33542 (10)	0.0381 (4)
H7	0.5390	0.4710	0.3001	0.046*
C8	0.61230 (12)	0.3907 (5)	0.41126 (10)	0.0339 (4)
C9	0.70294 (11)	0.4414 (4)	0.46533 (9)	0.0304 (4)
C10	0.96654 (14)	0.6382 (6)	0.63092 (11)	0.0451 (5)
H10	0.9774	0.5355	0.6799	0.054*
C11	0.45218 (13)	0.1914 (6)	0.39243 (13)	0.0477 (5)
H11A	0.4134	0.0738	0.4208	0.072*
H11B	0.4548	0.0613	0.3469	0.072*
H11C	0.4249	0.4110	0.3764	0.072*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0550 (4)	0.0636 (4)	0.0312 (3)	−0.0071 (2)	0.0116 (2)	0.00723 (19)
N1	0.0347 (8)	0.0368 (8)	0.0325 (7)	−0.0019 (6)	0.0132 (6)	−0.0004 (6)
O1	0.0409 (8)	0.0860 (13)	0.0560 (10)	−0.0244 (8)	0.0028 (7)	0.0043 (9)
O2	0.0321 (7)	0.0598 (10)	0.0421 (8)	−0.0124 (6)	0.0078 (6)	0.0026 (6)
C1	0.0373 (9)	0.0355 (9)	0.0288 (8)	−0.0012 (7)	0.0115 (6)	−0.0005 (7)
C2	0.0315 (9)	0.0369 (10)	0.0360 (9)	−0.0019 (7)	0.0088 (7)	−0.0028 (7)
C3	0.0311 (9)	0.0372 (9)	0.0377 (9)	−0.0035 (7)	0.0138 (7)	−0.0011 (7)
C4	0.0338 (9)	0.0318 (9)	0.0326 (8)	0.0006 (7)	0.0127 (7)	−0.0016 (7)
C5	0.0399 (10)	0.0411 (11)	0.0353 (10)	−0.0009 (8)	0.0157 (8)	0.0031 (7)
C6	0.0451 (10)	0.0443 (11)	0.0297 (9)	0.0047 (8)	0.0110 (7)	0.0032 (7)
C7	0.0359 (9)	0.0411 (10)	0.0358 (9)	0.0021 (8)	0.0062 (7)	−0.0036 (7)
C8	0.0312 (9)	0.0344 (10)	0.0372 (9)	−0.0005 (7)	0.0109 (7)	−0.0034 (7)
C9	0.0310 (8)	0.0310 (9)	0.0315 (8)	−0.0002 (7)	0.0121 (6)	−0.0024 (6)
C10	0.0403 (11)	0.0549 (12)	0.0376 (10)	−0.0038 (9)	0.0053 (8)	0.0011 (9)
C11	0.0304 (10)	0.0542 (13)	0.0553 (13)	−0.0076 (8)	0.0053 (8)	−0.0010 (9)

Geometric parameters (Å, °)

Cl1—C1	1.7536 (17)	C4—C9	1.425 (2)
N1—C1	1.294 (2)	C5—C6	1.354 (3)
N1—C9	1.365 (2)	C5—H5	0.9300
O1—C10	1.192 (3)	C6—C7	1.416 (3)
O2—C8	1.355 (2)	C6—H6	0.9300
O2—C11	1.429 (2)	C7—C8	1.371 (2)
C1—C2	1.423 (3)	C7—H7	0.9300
C2—C3	1.374 (2)	C8—C9	1.425 (2)
C2—C10	1.482 (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
C1—N1—C9	117.55 (15)	C7—C6—H6	119.2
C8—O2—C11	118.05 (15)	C8—C7—C6	120.64 (16)
N1—C1—C2	125.95 (16)	C8—C7—H7	119.7
N1—C1—Cl1	114.99 (13)	C6—C7—H7	119.7
C2—C1—Cl1	119.05 (13)	O2—C8—C7	125.91 (16)
C3—C2—C1	116.23 (15)	O2—C8—C9	114.72 (15)
C3—C2—C10	119.81 (16)	C7—C8—C9	119.37 (16)
C1—C2—C10	123.91 (16)	N1—C9—C8	118.58 (15)
C2—C3—C4	120.89 (16)	N1—C9—C4	122.33 (15)
C2—C3—H3	119.6	C8—C9—C4	119.09 (16)
C4—C3—H3	119.6	O1—C10—C2	123.71 (19)
C3—C4—C5	123.09 (16)	O1—C10—H10	118.1
C3—C4—C9	117.00 (16)	C2—C10—H10	118.1
C5—C4—C9	119.89 (16)	O2—C11—H11A	109.5
C6—C5—C4	119.43 (17)	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
C5—C6—C7	121.57 (17)	H11A—C11—H11C	109.5
C5—C6—H6	119.2	H11B—C11—H11C	109.5
C9—N1—C1—C2	0.5 (3)	C11—O2—C8—C9	176.32 (16)
C9—N1—C1—Cl1	179.85 (12)	C6—C7—C8—O2	−179.69 (18)
N1—C1—C2—C3	−1.7 (3)	C6—C7—C8—C9	0.6 (3)
Cl1—C1—C2—C3	179.00 (14)	C1—N1—C9—C8	−178.13 (16)
N1—C1—C2—C10	175.74 (18)	C1—N1—C9—C4	1.7 (3)
Cl1—C1—C2—C10	−3.6 (3)	O2—C8—C9—N1	0.5 (2)
C1—C2—C3—C4	0.6 (3)	C7—C8—C9—N1	−179.81 (16)
C10—C2—C3—C4	−176.92 (17)	O2—C8—C9—C4	−179.36 (16)
C2—C3—C4—C5	179.70 (17)	C7—C8—C9—C4	0.3 (3)
C2—C3—C4—C9	1.3 (3)	C3—C4—C9—N1	−2.6 (3)
C3—C4—C5—C6	−177.25 (17)	C5—C4—C9—N1	178.97 (16)
C9—C4—C5—C6	1.1 (3)	C3—C4—C9—C8	177.22 (16)
C4—C5—C6—C7	−0.1 (3)	C5—C4—C9—C8	−1.2 (3)
C5—C6—C7—C8	−0.8 (3)	C3—C2—C10—O1	9.2 (3)
C11—O2—C8—C7	−3.4 (3)	C1—C2—C10—O1	−168.2 (2)