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The title compound, C10H8ClNO, crystallizes in the centrosymmetric space group C2/c. The compound exists in the keto form in the crystalline state. The heterocyclic ring is not aromatic. The N atom is sp2 hybridized. The structure is stabilized by N—H...O intermolecular hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002574/cf6042sup1.cif
Contains datablocks 1, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002574/cf6042Isup2.hkl
Contains datablock I

CCDC reference: 159854

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.050
  • wR factor = 0.151
  • Data-to-parameter ratio = 13.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry




Comment top

Quinolines are ligands which are used as complexing agents for different metals (Hensen et al., 1999). The structure determination of the title compound, (I), was undertaken to study the effect of substitutions at the 2 and 3 positions on the quinolinone ring as well as the nature of hydrogen bonding. The torsion angles and the least-squares plane confirm that the quinolinone ring is planar with the largest out-of-plane displacement for C4 [0.051 (2) Å]. The exocyclic angles of C3—C2—C11 [124.4 (2)°] and C3—C4—O4 [124.4 (2)°] deviate significantly from the normal value of 120°. This may be due to the steric repulsion between the substituents at positions 2 and 3, and at 3 and 4 respectively. The C4O4 bond length [1.255 (3) Å] indicates a typical double-bond character and keto form of the compound in the crystalline state. In the non-aromatic heterocyclic ring, due to conjugation in N1—C2C3—C4O4, C3—C4 [1.421 (3) Å] shows the characteristic shortening of the bond from the normal value of 1.478 Å (Allen et al., 1987). In the absence of substituents at C2, the average bond distance of N1—C2 is 1.310 (3) Å in related structures (Dobson & Gerkin, 1999; Lokaj et al., 1999). In the present structure, due to the substitution of the methyl group at C2, there is a significant increase in the bond length N1—C2 [1.342 (3) Å] from the average value. The N atom is sp2 hybridized. The structure is stabilized by a linear intermolecular hydrogen bond N1—H1···O4i [symmetry code: (i) x, -y, z + 0.5]. The hydrogen-bond parameters are: N1—H1 = 0.89 Å, N1···O4i = 2.712 (2) Å, H1···O4i = 1.825 Å and N1—H1···O4i = 174°. All the other intermolecular interactions are van der Waals in nature.

Experimental top

2-Methyl-4-quinolone was treated with an equimolar amount of N-chlorosuccinimide in glacial acetic acid at 323–333 K for 30 min. The reaction mixture was poured over ice and the solid was filtered. It was washed with ice-cold water and dried over anhydrous calcium chloride (yield 75%). The compound was crystallized from ethanol by slow evaporation at 298–303 K.

Refinement top

All H atoms, except the methyl H atoms were located from difference Fourier maps and were included in the structure-factor calculations with isotropic displacement parameters equal to 1.1Ueq of their respective carrier atom, but their parameters were not refined. The methyl H atoms were fixed with HFIX options of the SHELX program, using the riding model. Uiso of methyl H atoms were taken as 1.5Ueq(C11).

Computing details top

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids.
3-chloro-2-methylquinolin-4-one top
Crystal data top
C10H8ClNOF(000) = 800
Mr = 193.62Dx = 1.443 Mg m3
Monoclinic, C2/cCu Kα radiation, λ = 1.54180 Å
a = 24.493 (4) ÅCell parameters from 25 reflections
b = 6.365 (2) Åθ = 20–30°
c = 12.859 (8) ŵ = 3.42 mm1
β = 117.240 (3)°T = 293 K
V = 1782.2 (13) Å3Plate, yellow
Z = 80.35 × 0.2 × 0.15 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
1440 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
Graphite monochromatorθmax = 68.0°, θmin = 4.1°
ω–2θ scansh = 029
Absorption correction: ψ scan
(North et al., 1968)
k = 07
Tmin = 0.320, Tmax = 0.603l = 1513
1661 measured reflections2 standard reflections every 120 min
1624 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0966P)2 + 1.8554P]
where P = (Fo2 + 2Fc2)/3
1624 reflections(Δ/σ)max = 0.002
118 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
C10H8ClNOV = 1782.2 (13) Å3
Mr = 193.62Z = 8
Monoclinic, C2/cCu Kα radiation
a = 24.493 (4) ŵ = 3.42 mm1
b = 6.365 (2) ÅT = 293 K
c = 12.859 (8) Å0.35 × 0.2 × 0.15 mm
β = 117.240 (3)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
1440 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.050
Tmin = 0.320, Tmax = 0.6032 standard reflections every 120 min
1661 measured reflections intensity decay: none
1624 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.151H-atom parameters constrained
S = 1.08Δρmax = 0.43 e Å3
1624 reflectionsΔρmin = 0.36 e Å3
118 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cl0.04456 (3)0.21977 (11)0.91307 (5)0.0538 (3)
O40.11936 (10)0.1608 (3)0.93680 (15)0.0548 (5)
N10.11141 (9)0.0026 (3)1.23448 (15)0.0370 (5)
C20.08088 (10)0.1205 (4)1.1385 (2)0.0355 (5)
C30.08300 (10)0.0666 (4)1.03717 (19)0.0358 (5)
C40.11546 (10)0.1112 (4)1.02766 (19)0.0364 (5)
C50.17490 (11)0.4268 (4)1.1327 (2)0.0419 (6)
C60.20278 (12)0.5444 (4)1.2321 (3)0.0489 (6)
C70.20264 (12)0.4770 (5)1.3352 (2)0.0526 (7)
C80.17326 (12)0.2953 (4)1.3373 (2)0.0476 (6)
C90.14292 (10)0.1762 (4)1.23524 (19)0.0346 (5)
C100.14455 (10)0.2394 (3)1.13238 (19)0.0333 (5)
C110.04653 (12)0.3056 (4)1.1508 (2)0.0464 (6)
H11A0.05170.31161.22940.070*
H11B0.00370.29171.09720.070*
H11C0.06220.43221.13380.070*
H10.11180.04961.30000.040*
H50.17380.47791.05300.045*
H60.21960.67191.22780.053*
H70.22110.56731.40600.056*
H80.17400.24451.41190.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0669 (5)0.0536 (4)0.0399 (4)0.0124 (3)0.0236 (3)0.0171 (3)
O40.0892 (14)0.0518 (11)0.0363 (10)0.0101 (10)0.0399 (10)0.0030 (8)
N10.0484 (11)0.0381 (10)0.0290 (9)0.0006 (8)0.0215 (8)0.0015 (8)
C20.0409 (11)0.0315 (11)0.0375 (12)0.0017 (9)0.0207 (9)0.0012 (9)
C30.0434 (11)0.0345 (12)0.0298 (11)0.0016 (9)0.0170 (9)0.0040 (9)
C40.0466 (12)0.0350 (11)0.0311 (11)0.0045 (9)0.0207 (9)0.0001 (9)
C50.0465 (12)0.0363 (12)0.0480 (13)0.0027 (10)0.0260 (10)0.0031 (10)
C60.0484 (13)0.0360 (13)0.0638 (16)0.0064 (10)0.0271 (12)0.0053 (12)
C70.0555 (15)0.0495 (15)0.0505 (16)0.0086 (12)0.0223 (12)0.0196 (12)
C80.0570 (15)0.0521 (15)0.0355 (13)0.0057 (12)0.0227 (11)0.0099 (11)
C90.0399 (11)0.0342 (11)0.0324 (11)0.0024 (9)0.0189 (9)0.0011 (9)
C100.0392 (11)0.0314 (11)0.0327 (12)0.0032 (8)0.0192 (9)0.0005 (8)
C110.0535 (15)0.0390 (13)0.0518 (15)0.0046 (11)0.0285 (12)0.0000 (11)
Geometric parameters (Å, º) top
Cl—C31.734 (2)C5—H51.064
O4—C41.255 (3)C6—C71.395 (4)
N1—C21.342 (3)C6—H60.923
N1—C91.373 (3)C7—C81.369 (4)
N1—H10.890C7—H70.994
C2—C31.371 (3)C8—C91.399 (3)
C2—C111.497 (3)C8—H81.004
C3—C41.421 (3)C9—C101.400 (3)
C4—C101.452 (3)C11—H11A0.960
C5—C61.364 (4)C11—H11B0.960
C5—C101.405 (3)C11—H11C0.960
C2—N1—C9123.03 (19)C8—C7—C6120.6 (2)
C2—N1—H1116.3C8—C7—H7119.5
C9—N1—H1120.6C6—C7—H7119.7
N1—C2—C3119.1 (2)C7—C8—C9119.8 (2)
N1—C2—C11116.5 (2)C7—C8—H8120.8
C3—C2—C11124.4 (2)C9—C8—H8119.4
C2—C3—C4123.2 (2)N1—C9—C8120.8 (2)
C2—C3—Cl119.55 (18)N1—C9—C10119.4 (2)
C4—C3—Cl117.27 (17)C8—C9—C10119.9 (2)
O4—C4—C3124.4 (2)C9—C10—C5119.0 (2)
O4—C4—C10120.5 (2)C9—C10—C4120.1 (2)
C3—C4—C10115.10 (19)C5—C10—C4121.0 (2)
C6—C5—C10120.4 (2)C2—C11—H11A109.5
C6—C5—H5121.1C2—C11—H11B109.5
C10—C5—H5118.5H11A—C11—H11B109.5
C5—C6—C7120.2 (2)C2—C11—H11C109.5
C5—C6—H6118.2H11A—C11—H11C109.5
C7—C6—H6121.5H11B—C11—H11C109.5
C9—N1—C2—C32.8 (3)C2—N1—C9—C100.9 (3)
C9—N1—C2—C11177.4 (2)C7—C8—C9—N1177.8 (2)
N1—C2—C3—C40.9 (3)C7—C8—C9—C102.2 (4)
C11—C2—C3—C4179.3 (2)N1—C9—C10—C5177.6 (2)
N1—C2—C3—Cl179.16 (16)C8—C9—C10—C52.4 (3)
C11—C2—C3—Cl0.6 (3)N1—C9—C10—C42.8 (3)
C2—C3—C4—O4178.1 (2)C8—C9—C10—C4177.2 (2)
Cl—C3—C4—O42.0 (3)C6—C5—C10—C90.6 (4)
C2—C3—C4—C102.5 (3)C6—C5—C10—C4179.1 (2)
Cl—C3—C4—C10177.38 (16)O4—C4—C10—C9176.3 (2)
C10—C5—C6—C71.5 (4)C3—C4—C10—C94.3 (3)
C5—C6—C7—C81.7 (4)O4—C4—C10—C53.3 (4)
C6—C7—C8—C90.2 (4)C3—C4—C10—C5176.0 (2)
C2—N1—C9—C8179.0 (2)

Experimental details

Crystal data
Chemical formulaC10H8ClNO
Mr193.62
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)24.493 (4), 6.365 (2), 12.859 (8)
β (°) 117.240 (3)
V3)1782.2 (13)
Z8
Radiation typeCu Kα
µ (mm1)3.42
Crystal size (mm)0.35 × 0.2 × 0.15
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.320, 0.603
No. of measured, independent and
observed [I > 2σ(I)] reflections
1661, 1624, 1440
Rint0.050
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.151, 1.08
No. of reflections1624
No. of parameters118
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.43, 0.36

Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
N1—C91.373 (3)C5—C101.405 (3)
C5—C61.364 (4)C9—C101.400 (3)
N1—C2—C3119.1 (2)N1—C9—C8120.8 (2)
N1—C2—C11116.5 (2)N1—C9—C10119.4 (2)
C2—C3—Cl119.55 (18)C9—C10—C5119.0 (2)
O4—C4—C3124.4 (2)C9—C10—C4120.1 (2)
C9—N1—C2—C32.8 (3)Cl—C3—C4—C10177.38 (16)
N1—C2—C3—C40.9 (3)C7—C8—C9—C102.2 (4)
C2—C3—C4—O4178.1 (2)O4—C4—C10—C9176.3 (2)
 

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