Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801002574/cf6042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801002574/cf6042Isup2.hkl |
CCDC reference: 159854
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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.
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).
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.
C10H8ClNO | F(000) = 800 |
Mr = 193.62 | Dx = 1.443 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54180 Å |
a = 24.493 (4) Å | Cell parameters from 25 reflections |
b = 6.365 (2) Å | θ = 20–30° |
c = 12.859 (8) Å | µ = 3.42 mm−1 |
β = 117.240 (3)° | T = 293 K |
V = 1782.2 (13) Å3 | Plate, yellow |
Z = 8 | 0.35 × 0.2 × 0.15 mm |
Enraf-Nonius CAD-4 diffractometer | 1440 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 68.0°, θmin = 4.1° |
ω–2θ scans | h = 0→29 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→7 |
Tmin = 0.320, Tmax = 0.603 | l = −15→13 |
1661 measured reflections | 2 standard reflections every 120 min |
1624 independent reflections | intensity decay: none |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.151 | H-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 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C10H8ClNO | V = 1782.2 (13) Å3 |
Mr = 193.62 | Z = 8 |
Monoclinic, C2/c | Cu Kα radiation |
a = 24.493 (4) Å | µ = 3.42 mm−1 |
b = 6.365 (2) Å | T = 293 K |
c = 12.859 (8) Å | 0.35 × 0.2 × 0.15 mm |
β = 117.240 (3)° |
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 = 0.603 | 2 standard reflections every 120 min |
1661 measured reflections | intensity decay: none |
1624 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.151 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.43 e Å−3 |
1624 reflections | Δρmin = −0.36 e Å−3 |
118 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cl | 0.04456 (3) | 0.21977 (11) | 0.91307 (5) | 0.0538 (3) | |
O4 | 0.11936 (10) | −0.1608 (3) | 0.93680 (15) | 0.0548 (5) | |
N1 | 0.11141 (9) | 0.0026 (3) | 1.23448 (15) | 0.0370 (5) | |
C2 | 0.08088 (10) | 0.1205 (4) | 1.1385 (2) | 0.0355 (5) | |
C3 | 0.08300 (10) | 0.0666 (4) | 1.03717 (19) | 0.0358 (5) | |
C4 | 0.11546 (10) | −0.1112 (4) | 1.02766 (19) | 0.0364 (5) | |
C5 | 0.17490 (11) | −0.4268 (4) | 1.1327 (2) | 0.0419 (6) | |
C6 | 0.20278 (12) | −0.5444 (4) | 1.2321 (3) | 0.0489 (6) | |
C7 | 0.20264 (12) | −0.4770 (5) | 1.3352 (2) | 0.0526 (7) | |
C8 | 0.17326 (12) | −0.2953 (4) | 1.3373 (2) | 0.0476 (6) | |
C9 | 0.14292 (10) | −0.1762 (4) | 1.23524 (19) | 0.0346 (5) | |
C10 | 0.14455 (10) | −0.2394 (3) | 1.13238 (19) | 0.0333 (5) | |
C11 | 0.04653 (12) | 0.3056 (4) | 1.1508 (2) | 0.0464 (6) | |
H11A | 0.0517 | 0.3116 | 1.2294 | 0.070* | |
H11B | 0.0037 | 0.2917 | 1.0972 | 0.070* | |
H11C | 0.0622 | 0.4322 | 1.1338 | 0.070* | |
H1 | 0.1118 | 0.0496 | 1.3000 | 0.040* | |
H5 | 0.1738 | −0.4779 | 1.0530 | 0.045* | |
H6 | 0.2196 | −0.6719 | 1.2278 | 0.053* | |
H7 | 0.2211 | −0.5673 | 1.4060 | 0.056* | |
H8 | 0.1740 | −0.2445 | 1.4119 | 0.051* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl | 0.0669 (5) | 0.0536 (4) | 0.0399 (4) | 0.0124 (3) | 0.0236 (3) | 0.0171 (3) |
O4 | 0.0892 (14) | 0.0518 (11) | 0.0363 (10) | 0.0101 (10) | 0.0399 (10) | 0.0030 (8) |
N1 | 0.0484 (11) | 0.0381 (10) | 0.0290 (9) | 0.0006 (8) | 0.0215 (8) | −0.0015 (8) |
C2 | 0.0409 (11) | 0.0315 (11) | 0.0375 (12) | −0.0017 (9) | 0.0207 (9) | 0.0012 (9) |
C3 | 0.0434 (11) | 0.0345 (12) | 0.0298 (11) | −0.0016 (9) | 0.0170 (9) | 0.0040 (9) |
C4 | 0.0466 (12) | 0.0350 (11) | 0.0311 (11) | −0.0045 (9) | 0.0207 (9) | 0.0001 (9) |
C5 | 0.0465 (12) | 0.0363 (12) | 0.0480 (13) | −0.0027 (10) | 0.0260 (10) | −0.0031 (10) |
C6 | 0.0484 (13) | 0.0360 (13) | 0.0638 (16) | 0.0064 (10) | 0.0271 (12) | 0.0053 (12) |
C7 | 0.0555 (15) | 0.0495 (15) | 0.0505 (16) | 0.0086 (12) | 0.0223 (12) | 0.0196 (12) |
C8 | 0.0570 (15) | 0.0521 (15) | 0.0355 (13) | 0.0057 (12) | 0.0227 (11) | 0.0099 (11) |
C9 | 0.0399 (11) | 0.0342 (11) | 0.0324 (11) | −0.0024 (9) | 0.0189 (9) | 0.0011 (9) |
C10 | 0.0392 (11) | 0.0314 (11) | 0.0327 (12) | −0.0032 (8) | 0.0192 (9) | −0.0005 (8) |
C11 | 0.0535 (15) | 0.0390 (13) | 0.0518 (15) | 0.0046 (11) | 0.0285 (12) | 0.0000 (11) |
Cl—C3 | 1.734 (2) | C5—H5 | 1.064 |
O4—C4 | 1.255 (3) | C6—C7 | 1.395 (4) |
N1—C2 | 1.342 (3) | C6—H6 | 0.923 |
N1—C9 | 1.373 (3) | C7—C8 | 1.369 (4) |
N1—H1 | 0.890 | C7—H7 | 0.994 |
C2—C3 | 1.371 (3) | C8—C9 | 1.399 (3) |
C2—C11 | 1.497 (3) | C8—H8 | 1.004 |
C3—C4 | 1.421 (3) | C9—C10 | 1.400 (3) |
C4—C10 | 1.452 (3) | C11—H11A | 0.960 |
C5—C6 | 1.364 (4) | C11—H11B | 0.960 |
C5—C10 | 1.405 (3) | C11—H11C | 0.960 |
C2—N1—C9 | 123.03 (19) | C8—C7—C6 | 120.6 (2) |
C2—N1—H1 | 116.3 | C8—C7—H7 | 119.5 |
C9—N1—H1 | 120.6 | C6—C7—H7 | 119.7 |
N1—C2—C3 | 119.1 (2) | C7—C8—C9 | 119.8 (2) |
N1—C2—C11 | 116.5 (2) | C7—C8—H8 | 120.8 |
C3—C2—C11 | 124.4 (2) | C9—C8—H8 | 119.4 |
C2—C3—C4 | 123.2 (2) | N1—C9—C8 | 120.8 (2) |
C2—C3—Cl | 119.55 (18) | N1—C9—C10 | 119.4 (2) |
C4—C3—Cl | 117.27 (17) | C8—C9—C10 | 119.9 (2) |
O4—C4—C3 | 124.4 (2) | C9—C10—C5 | 119.0 (2) |
O4—C4—C10 | 120.5 (2) | C9—C10—C4 | 120.1 (2) |
C3—C4—C10 | 115.10 (19) | C5—C10—C4 | 121.0 (2) |
C6—C5—C10 | 120.4 (2) | C2—C11—H11A | 109.5 |
C6—C5—H5 | 121.1 | C2—C11—H11B | 109.5 |
C10—C5—H5 | 118.5 | H11A—C11—H11B | 109.5 |
C5—C6—C7 | 120.2 (2) | C2—C11—H11C | 109.5 |
C5—C6—H6 | 118.2 | H11A—C11—H11C | 109.5 |
C7—C6—H6 | 121.5 | H11B—C11—H11C | 109.5 |
C9—N1—C2—C3 | −2.8 (3) | C2—N1—C9—C10 | 0.9 (3) |
C9—N1—C2—C11 | 177.4 (2) | C7—C8—C9—N1 | 177.8 (2) |
N1—C2—C3—C4 | 0.9 (3) | C7—C8—C9—C10 | −2.2 (4) |
C11—C2—C3—C4 | −179.3 (2) | N1—C9—C10—C5 | −177.6 (2) |
N1—C2—C3—Cl | −179.16 (16) | C8—C9—C10—C5 | 2.4 (3) |
C11—C2—C3—Cl | 0.6 (3) | N1—C9—C10—C4 | 2.8 (3) |
C2—C3—C4—O4 | −178.1 (2) | C8—C9—C10—C4 | −177.2 (2) |
Cl—C3—C4—O4 | 2.0 (3) | C6—C5—C10—C9 | −0.6 (4) |
C2—C3—C4—C10 | 2.5 (3) | C6—C5—C10—C4 | 179.1 (2) |
Cl—C3—C4—C10 | −177.38 (16) | O4—C4—C10—C9 | 176.3 (2) |
C10—C5—C6—C7 | −1.5 (4) | C3—C4—C10—C9 | −4.3 (3) |
C5—C6—C7—C8 | 1.7 (4) | O4—C4—C10—C5 | −3.3 (4) |
C6—C7—C8—C9 | 0.2 (4) | C3—C4—C10—C5 | 176.0 (2) |
C2—N1—C9—C8 | −179.0 (2) |
Experimental details
Crystal data | |
Chemical formula | C10H8ClNO |
Mr | 193.62 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 24.493 (4), 6.365 (2), 12.859 (8) |
β (°) | 117.240 (3) |
V (Å3) | 1782.2 (13) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 3.42 |
Crystal size (mm) | 0.35 × 0.2 × 0.15 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.320, 0.603 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1661, 1624, 1440 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.601 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.151, 1.08 |
No. of reflections | 1624 |
No. of parameters | 118 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
N1—C9 | 1.373 (3) | C5—C10 | 1.405 (3) |
C5—C6 | 1.364 (4) | C9—C10 | 1.400 (3) |
N1—C2—C3 | 119.1 (2) | N1—C9—C8 | 120.8 (2) |
N1—C2—C11 | 116.5 (2) | N1—C9—C10 | 119.4 (2) |
C2—C3—Cl | 119.55 (18) | C9—C10—C5 | 119.0 (2) |
O4—C4—C3 | 124.4 (2) | C9—C10—C4 | 120.1 (2) |
C9—N1—C2—C3 | −2.8 (3) | Cl—C3—C4—C10 | −177.38 (16) |
N1—C2—C3—C4 | 0.9 (3) | C7—C8—C9—C10 | −2.2 (4) |
C2—C3—C4—O4 | −178.1 (2) | O4—C4—C10—C9 | 176.3 (2) |
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 C4═O4 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—C2═C3—C4═O4, 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.