2-Chloro-7-methyl­quinoline-3-carbaldehyde

Abstract

The quinoline fused-ring system of the title compound, C₁₁H₈ClNO, is planar (r.m.s. deviation = 0.007 Å); the formyl group is bent slightly out of the plane [C—C—C—O torsion angles = −9.6 (5) and 170.4 (3)°].

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

• Monoclinic,

• a = 15.458 (3) Å

• b = 3.9382 (8) Å

• c = 16.923 (3) Å

• β = 112.854 (3)°

• V = 949.3 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 0.36 mm⁻¹

• T = 290 K

• 0.24 × 0.18 × 0.06 mm

Data collection

• Bruker SMART area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.918, T _max = 0.979

• 6484 measured reflections

• 1796 independent reflections

• 1356 reflections with I > 2σ(I)

• R _int = 0.042

Refinement

• R[F ² > 2σ(F ²)] = 0.078

• wR(F ²) = 0.209

• S = 1.13

• 1796 reflections

• 128 parameters

• H-atom parameters constrained

• Δρ_max = 0.78 e Å⁻³

• Δρ_min = −0.49 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-(3-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.

Refinement

Carbon-bound 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.

Thermal ellipsoid plot (Barbour, 2001) of C11H8ClNO at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C11H8ClNO	F(000) = 424
Mr = 205.63	Dx = 1.439 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 973 reflections
a = 15.458 (3) Å	θ = 1.3–24.9°
b = 3.9382 (8) Å	µ = 0.36 mm−1
c = 16.923 (3) Å	T = 290 K
β = 112.854 (3)°	Block, colorless
V = 949.3 (3) Å3	0.24 × 0.18 × 0.06 mm
Z = 4

Data collection

Bruker SMART area-detector diffractometer	1796 independent reflections
Radiation source: fine-focus sealed tube	1356 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 25.7°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
Tmin = 0.918, Tmax = 0.979	k = −4→4
6484 measured reflections	l = −20→20

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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.209	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.1371P)2] where P = (Fo2 + 2Fc2)/3
1796 reflections	(Δ/σ)max = 0.001
128 parameters	Δρmax = 0.78 e Å−3
0 restraints	Δρmin = −0.49 e Å−3

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

	x	y	z	Uiso*/Ueq
Cl1	0.37647 (6)	0.6903 (3)	0.18658 (6)	0.0603 (4)
O1	0.36833 (17)	0.1214 (8)	0.39875 (18)	0.0705 (9)
N1	0.55664 (19)	0.6719 (7)	0.27097 (16)	0.0402 (7)
C1	0.4781 (2)	0.5835 (8)	0.27548 (19)	0.0393 (7)
C2	0.4683 (2)	0.4068 (8)	0.34482 (19)	0.0383 (7)
C3	0.5497 (2)	0.3312 (8)	0.4129 (2)	0.0387 (7)
H3	0.5468	0.2182	0.4601	0.046*
C4	0.6373 (2)	0.4210 (7)	0.41281 (18)	0.0347 (7)
C5	0.7243 (2)	0.3490 (8)	0.48060 (19)	0.0407 (8)
H5	0.7253	0.2376	0.5294	0.049*
C6	0.8064 (2)	0.4414 (8)	0.47489 (19)	0.0424 (8)
H6	0.8628	0.3923	0.5201	0.051*
C7	0.8080 (2)	0.6125 (7)	0.4009 (2)	0.0394 (8)
C8	0.7248 (2)	0.6851 (8)	0.3354 (2)	0.0391 (7)
H8	0.7252	0.7978	0.2872	0.047*
C9	0.6379 (2)	0.5927 (7)	0.33897 (18)	0.0341 (7)
C10	0.3769 (2)	0.3059 (9)	0.3458 (2)	0.0503 (9)
H10	0.3228	0.3900	0.3029	0.060*
C11	0.9001 (3)	0.7114 (9)	0.3968 (2)	0.0523 (9)
H11A	0.8906	0.9001	0.3584	0.078*
H11B	0.9248	0.5226	0.3764	0.078*
H11C	0.9436	0.7746	0.4530	0.078*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0499 (6)	0.0826 (8)	0.0457 (6)	0.0050 (4)	0.0157 (4)	0.0154 (4)
O1	0.0512 (17)	0.103 (2)	0.0731 (18)	−0.0030 (14)	0.0416 (15)	0.0286 (15)
N1	0.0478 (16)	0.0474 (15)	0.0341 (14)	0.0010 (12)	0.0252 (13)	0.0033 (10)
C1	0.0427 (18)	0.0452 (17)	0.0380 (16)	0.0017 (13)	0.0245 (14)	0.0012 (13)
C2	0.0407 (18)	0.0452 (17)	0.0395 (17)	0.0026 (12)	0.0272 (14)	0.0014 (12)
C3	0.0476 (19)	0.0439 (17)	0.0383 (16)	0.0018 (13)	0.0316 (15)	0.0017 (12)
C4	0.0424 (17)	0.0396 (15)	0.0323 (15)	0.0025 (12)	0.0257 (13)	−0.0005 (11)
C5	0.0439 (18)	0.0549 (19)	0.0338 (16)	0.0035 (14)	0.0267 (14)	0.0011 (13)
C6	0.0390 (17)	0.0560 (19)	0.0386 (17)	0.0053 (14)	0.0221 (14)	−0.0053 (14)
C7	0.0467 (19)	0.0403 (16)	0.0449 (18)	−0.0047 (13)	0.0328 (16)	−0.0095 (12)
C8	0.0477 (19)	0.0440 (17)	0.0400 (17)	−0.0032 (13)	0.0327 (15)	−0.0016 (12)
C9	0.0423 (17)	0.0391 (15)	0.0322 (15)	−0.0007 (12)	0.0268 (13)	−0.0019 (11)
C10	0.0388 (19)	0.065 (2)	0.055 (2)	0.0019 (15)	0.0272 (17)	0.0066 (17)
C11	0.0469 (19)	0.060 (2)	0.063 (2)	−0.0075 (15)	0.0351 (17)	−0.0042 (16)

Geometric parameters (Å, °)

Cl1—C1	1.753 (3)	C5—H5	0.9300
O1—C10	1.200 (4)	C6—C7	1.430 (4)
N1—C1	1.293 (4)	C6—H6	0.9300
N1—C9	1.370 (4)	C7—C8	1.363 (4)
C1—C2	1.422 (4)	C7—C11	1.502 (5)
C2—C3	1.369 (4)	C8—C9	1.416 (4)
C2—C10	1.473 (4)	C8—H8	0.9300
C3—C4	1.400 (4)	C10—H10	0.9300
C3—H3	0.9300	C11—H11A	0.9600
C4—C5	1.417 (4)	C11—H11B	0.9600
C4—C9	1.424 (4)	C11—H11C	0.9600
C5—C6	1.359 (4)
C1—N1—C9	117.7 (3)	C8—C7—C6	118.6 (3)
N1—C1—C2	125.7 (3)	C8—C7—C11	121.3 (3)
N1—C1—Cl1	115.7 (2)	C6—C7—C11	120.1 (3)
C2—C1—Cl1	118.5 (2)	C7—C8—C9	121.5 (3)
C3—C2—C1	116.3 (3)	C7—C8—H8	119.3
C3—C2—C10	120.2 (3)	C9—C8—H8	119.3
C1—C2—C10	123.5 (3)	N1—C9—C8	118.8 (3)
C2—C3—C4	121.2 (3)	N1—C9—C4	121.9 (3)
C2—C3—H3	119.4	C8—C9—C4	119.3 (3)
C4—C3—H3	119.4	O1—C10—C2	123.8 (3)
C3—C4—C5	124.3 (3)	O1—C10—H10	118.1
C3—C4—C9	117.2 (3)	C2—C10—H10	118.1
C5—C4—C9	118.5 (3)	C7—C11—H11A	109.5
C6—C5—C4	120.5 (3)	C7—C11—H11B	109.5
C6—C5—H5	119.7	H11A—C11—H11B	109.5
C4—C5—H5	119.7	C7—C11—H11C	109.5
C5—C6—C7	121.5 (3)	H11A—C11—H11C	109.5
C5—C6—H6	119.3	H11B—C11—H11C	109.5
C7—C6—H6	119.3
C9—N1—C1—C2	−0.7 (5)	C5—C6—C7—C11	179.9 (3)
C9—N1—C1—Cl1	−179.8 (2)	C6—C7—C8—C9	−0.5 (4)
N1—C1—C2—C3	1.3 (5)	C11—C7—C8—C9	−180.0 (3)
Cl1—C1—C2—C3	−179.6 (2)	C1—N1—C9—C8	179.6 (3)
N1—C1—C2—C10	−178.7 (3)	C1—N1—C9—C4	−0.4 (4)
Cl1—C1—C2—C10	0.5 (4)	C7—C8—C9—N1	−179.8 (3)
C1—C2—C3—C4	−0.8 (4)	C7—C8—C9—C4	0.2 (4)
C10—C2—C3—C4	179.2 (3)	C3—C4—C9—N1	0.8 (4)
C2—C3—C4—C5	−179.5 (3)	C5—C4—C9—N1	−179.8 (3)
C2—C3—C4—C9	−0.2 (4)	C3—C4—C9—C8	−179.2 (3)
C3—C4—C5—C6	179.1 (3)	C5—C4—C9—C8	0.1 (4)
C9—C4—C5—C6	−0.2 (4)	C3—C2—C10—O1	−9.6 (5)
C4—C5—C6—C7	−0.1 (5)	C1—C2—C10—O1	170.4 (3)
C5—C6—C7—C8	0.5 (5)