3-Chloro-4-methyl­quinolin-2(1H)-one

Abstract

The title compound, C₁₀H₈ClNO, is almost planar (r.m.s. deviation for the 13 non-H atoms = 0.023 Å). In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R ₂ ²(8) rings. Weak aromatic π–π stacking inter­actions [centroid–centroid distance = 3.7622 (12) Å] also occur.

Related literature  

For the biological activity of quinoline, see: Michael et al. (1996 ▶). For the synthesis, see: Hodgkinson & Staskun (1969 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For a related structure, see: Vasuki et al. (2001) ▶. For bond-length data, see: Allen et al. (1987 ▶).

Experimental  

Crystal data  

• C₁₀H₈ClNO

• M _r = 193.62

• Monoclinic,

• a = 3.9361 (2) Å

• b = 12.9239 (6) Å

• c = 17.1019 (7) Å

• β = 100.197 (4)°

• V = 856.23 (7) ų

• Z = 4

• Cu Kα radiation

• μ = 3.56 mm⁻¹

• T = 296 K

• 0.92 × 0.10 × 0.10 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.138, T _max = 0.720

• 5522 measured reflections

• 1434 independent reflections

• 1178 reflections with I > 2σ(I)

• R _int = 0.040

Refinement  

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.105

• S = 1.00

• 1434 reflections

• 120 parameters

• H-atom parameters constrained

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812009889/hb6671Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.93	1.91	2.816 (2)	166

Symmetry code: (i) .

supplementary crystallographic information

Comment

For the previous reports of the chemistry and the biological activity of quinolines, see Michael et al. (1996).

In the title compound (Fig. 1), the quinoline ring (N1/C1–C9) is essentially planar with a maximum deviation of 0.012 (2) Å at atom C1. The bond lengths (Allen et al., 1987) and angles are within normal ranges are comparable to the related structure (Vasuki et al., 2001).

In the crystal structure (Fig. 2), the adjacent molecules are linked via pair of N1—H1···O1 (Table 1) hydrogen bonds, forming dimers with an R₂² (8) ring motif (Bernstein et al., 1995). The crystal structure is further stabilized by weak π—π interactions between the benzene ring (Cg1; C4–C9) and quinoline ring (Cg2; N1/C1–C9). [Cg1···Cg2 = 3.7622 (12) Å; 1+x, y, z].

Experimental

This compound was prepared according to the reported method (Hodgkinson & Staskun, 1969). Colorless needles of the title compound were grown from a mixed solution of EtOH/DMF (V/V = 2/1) by slow evaporation at room temperature.

Refinement

Atom H1 was located from the difference map and was fixed at their found positions with U_iso(H) = 1.2 U_eq(N) [N–H = 0.9256 Å]. The remaining H atoms were positioned geometrically and refined using a riding model with U_iso(H) = 1.2 or 1.5U_eq(C) (C—H = 0.93 and 0.96 Å). A rotating group model was applied to the methyl group.

Figures

Fig. 1.

The molecular structure of the title compound, showing 30% probability displacement ellipsoids.

Fig. 2.

The crystal packing of the title compound, viewed along the b axis. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

Crystal data

C10H8ClNO	F(000) = 400
Mr = 193.62	Dx = 1.502 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 615 reflections
a = 3.9361 (2) Å	θ = 4.3–63.6°
b = 12.9239 (6) Å	µ = 3.56 mm−1
c = 17.1019 (7) Å	T = 296 K
β = 100.197 (4)°	Needle, colourless
V = 856.23 (7) Å3	0.92 × 0.10 × 0.10 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	1434 independent reflections
Radiation source: fine-focus sealed tube	1178 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 64.9°, θmin = 4.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −4→3
Tmin = 0.138, Tmax = 0.720	k = −15→14
5522 measured reflections	l = −20→17

Refinement

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)] = 0.037	H-atom parameters constrained
wR(F2) = 0.105	w = 1/[σ2(Fo2) + (0.0755P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
1434 reflections	Δρmax = 0.18 e Å−3
120 parameters	Δρmin = −0.21 e Å−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0031 (9)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Cl1	1.04066 (14)	0.51266 (4)	0.76645 (3)	0.0516 (2)
O1	1.0673 (4)	0.46152 (12)	0.60239 (9)	0.0560 (4)
N1	0.7804 (4)	0.60196 (13)	0.54512 (9)	0.0422 (4)
H1	0.7928	0.5780	0.4947	0.051*
C1	0.9152 (5)	0.54435 (15)	0.60939 (12)	0.0414 (4)
C2	0.8689 (5)	0.58782 (15)	0.68546 (11)	0.0386 (4)
C3	0.7149 (4)	0.68001 (14)	0.69302 (11)	0.0371 (4)
C4	0.5836 (5)	0.73765 (14)	0.62192 (11)	0.0368 (4)
C5	0.4234 (5)	0.83478 (16)	0.62245 (12)	0.0446 (5)
H5A	0.3935	0.8637	0.6706	0.054*
C6	0.3104 (6)	0.88763 (17)	0.55307 (14)	0.0529 (6)
H6A	0.2094	0.9525	0.5546	0.064*
C7	0.3468 (6)	0.84441 (18)	0.48054 (14)	0.0552 (6)
H7A	0.2690	0.8804	0.4337	0.066*
C8	0.4965 (5)	0.74913 (17)	0.47760 (12)	0.0477 (5)
H8A	0.5166	0.7198	0.4290	0.057*
C9	0.6184 (5)	0.69643 (15)	0.54803 (11)	0.0385 (4)
C10	0.6782 (6)	0.72335 (16)	0.77284 (11)	0.0468 (5)
H10A	0.7537	0.6728	0.8133	0.070*
H10B	0.4407	0.7403	0.7728	0.070*
H10C	0.8168	0.7846	0.7833	0.070*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.0660 (4)	0.0475 (3)	0.0416 (3)	0.0056 (2)	0.0105 (2)	0.0074 (2)
O1	0.0806 (11)	0.0439 (9)	0.0462 (9)	0.0171 (8)	0.0183 (7)	−0.0027 (7)
N1	0.0548 (10)	0.0398 (9)	0.0339 (9)	0.0011 (7)	0.0134 (7)	−0.0035 (7)
C1	0.0486 (11)	0.0363 (10)	0.0412 (10)	−0.0011 (8)	0.0129 (8)	−0.0036 (8)
C2	0.0443 (10)	0.0376 (10)	0.0351 (10)	−0.0038 (7)	0.0104 (7)	0.0000 (8)
C3	0.0386 (10)	0.0392 (10)	0.0349 (10)	−0.0065 (7)	0.0105 (7)	−0.0042 (8)
C4	0.0369 (10)	0.0363 (10)	0.0382 (10)	−0.0046 (7)	0.0090 (7)	−0.0041 (8)
C5	0.0451 (11)	0.0415 (11)	0.0474 (12)	−0.0002 (8)	0.0086 (8)	−0.0062 (9)
C6	0.0528 (12)	0.0430 (11)	0.0610 (14)	0.0065 (9)	0.0046 (10)	0.0014 (10)
C7	0.0574 (13)	0.0547 (14)	0.0506 (13)	0.0009 (10)	0.0014 (10)	0.0121 (10)
C8	0.0559 (12)	0.0498 (12)	0.0374 (11)	−0.0005 (9)	0.0084 (8)	0.0017 (9)
C9	0.0395 (10)	0.0389 (10)	0.0380 (10)	−0.0045 (7)	0.0096 (7)	−0.0026 (8)
C10	0.0551 (12)	0.0491 (12)	0.0380 (10)	0.0024 (9)	0.0128 (8)	−0.0080 (9)

Geometric parameters (Å, º)

Cl1—C2	1.728 (2)	C5—C6	1.373 (3)
O1—C1	1.243 (3)	C5—H5A	0.9300
N1—C1	1.355 (3)	C6—C7	1.391 (3)
N1—C9	1.382 (3)	C6—H6A	0.9300
N1—H1	0.9256	C7—C8	1.370 (3)
C1—C2	1.458 (3)	C7—H7A	0.9300
C2—C3	1.353 (3)	C8—C9	1.393 (3)
C3—C4	1.442 (3)	C8—H8A	0.9300
C3—C10	1.506 (2)	C10—H10A	0.9600
C4—C9	1.400 (3)	C10—H10B	0.9600
C4—C5	1.406 (3)	C10—H10C	0.9600
C1—N1—C9	124.95 (17)	C5—C6—C7	120.2 (2)
C1—N1—H1	119.6	C5—C6—H6A	119.9
C9—N1—H1	115.4	C7—C6—H6A	119.9
O1—C1—N1	121.42 (18)	C8—C7—C6	120.4 (2)
O1—C1—C2	123.80 (19)	C8—C7—H7A	119.8
N1—C1—C2	114.78 (17)	C6—C7—H7A	119.8
C3—C2—C1	123.60 (18)	C7—C8—C9	119.5 (2)
C3—C2—Cl1	122.45 (15)	C7—C8—H8A	120.3
C1—C2—Cl1	113.93 (15)	C9—C8—H8A	120.3
C2—C3—C4	118.30 (17)	N1—C9—C8	119.43 (18)
C2—C3—C10	122.04 (18)	N1—C9—C4	119.21 (18)
C4—C3—C10	119.65 (17)	C8—C9—C4	121.37 (19)
C9—C4—C5	117.48 (18)	C3—C10—H10A	109.5
C9—C4—C3	119.13 (18)	C3—C10—H10B	109.5
C5—C4—C3	123.38 (18)	H10A—C10—H10B	109.5
C6—C5—C4	121.0 (2)	C3—C10—H10C	109.5
C6—C5—H5A	119.5	H10A—C10—H10C	109.5
C4—C5—H5A	119.5	H10B—C10—H10C	109.5
C9—N1—C1—O1	−177.64 (19)	C9—C4—C5—C6	−0.9 (3)
C9—N1—C1—C2	1.9 (3)	C3—C4—C5—C6	178.36 (19)
O1—C1—C2—C3	177.3 (2)	C4—C5—C6—C7	1.4 (3)
N1—C1—C2—C3	−2.2 (3)	C5—C6—C7—C8	−0.3 (3)
O1—C1—C2—Cl1	−0.8 (3)	C6—C7—C8—C9	−1.2 (3)
N1—C1—C2—Cl1	179.65 (14)	C1—N1—C9—C8	178.74 (18)
C1—C2—C3—C4	1.2 (3)	C1—N1—C9—C4	−0.6 (3)
Cl1—C2—C3—C4	179.19 (13)	C7—C8—C9—N1	−177.72 (19)
C1—C2—C3—C10	−178.76 (18)	C7—C8—C9—C4	1.6 (3)
Cl1—C2—C3—C10	−0.7 (3)	C5—C4—C9—N1	178.79 (17)
C2—C3—C4—C9	0.2 (3)	C3—C4—C9—N1	−0.5 (3)
C10—C3—C4—C9	−179.84 (16)	C5—C4—C9—C8	−0.5 (3)
C2—C3—C4—C5	−179.06 (18)	C3—C4—C9—C8	−179.88 (17)
C10—C3—C4—C5	0.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.93	1.91	2.816 (2)	166

Symmetry code: (i) −x+2, −y+1, −z+1.