Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039322/lh6544sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039322/lh6544Isup2.hkl |
CCDC reference: 296604
One drop of concentrated sulfuric acid was added to a mixture of 2-methyl-8-hydroxyquinoline (15.9 g, 0.1 mol) and acetic anhydride (10.2 g, 9.4 ml, 0.1 mol) in a 250 ml Erlenmeyer flask. The mixture was warmed rapidly and stirred gently by hand. After 5 min, the clear solution was poured onto crushed ice (about 200 ml). The solid was filtered off and washed with water (200 ml). The compound obtained was 2-methyl-8-acetoxyquionoline (18.6 g, 93%; m.p. 394–395 K). To a dioxane supension (40 ml) of freshly sublimed selenium dioxide (5.8 g), a dioxane solution (50 ml) of 2-methyl-8-acetoxyquionoline (11.4 g) was added with stirring over a water bath at 323–328 K for 3 h. The mixture was filtered after being allowed to stand for 2 h. The dioxane was distilled off to give light-yellow [Colourless below?] crystals of (I) (9.0 g; m.p. 367–368 K).
H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93–0.96 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
Fig. 1. The structure of (I). Displacement ellipsoids are drawn at the 30% probability level. |
C12H9NO3 | F(000) = 896 |
Mr = 215.20 | Dx = 1.341 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3212 reflections |
a = 19.743 (3) Å | θ = 2.3–24.9° |
b = 7.863 (1) Å | µ = 0.10 mm−1 |
c = 14.771 (2) Å | T = 298 K |
β = 111.66 (2)° | Block, colourless |
V = 2131.1 (6) Å3 | 0.53 × 0.46 × 0.41 mm |
Z = 8 |
Bruker SMART CCD area-detector diffractometer | 2315 independent reflections |
Radiation source: fine-focus sealed tube | 1225 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
ω scans | θmax = 27.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −24→25 |
Tmin = 0.950, Tmax = 0.961 | k = −8→10 |
6309 measured reflections | l = −18→18 |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.134 | w = 1/[σ2(Fo2) + (0.0577P)2 + 0.2105P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
2315 reflections | Δρmax = 0.18 e Å−3 |
147 parameters | Δρmin = −0.15 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997a), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0073 (10) |
C12H9NO3 | V = 2131.1 (6) Å3 |
Mr = 215.20 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.743 (3) Å | µ = 0.10 mm−1 |
b = 7.863 (1) Å | T = 298 K |
c = 14.771 (2) Å | 0.53 × 0.46 × 0.41 mm |
β = 111.66 (2)° |
Bruker SMART CCD area-detector diffractometer | 2315 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1225 reflections with I > 2σ(I) |
Tmin = 0.950, Tmax = 0.961 | Rint = 0.045 |
6309 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.134 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.18 e Å−3 |
2315 reflections | Δρmin = −0.15 e Å−3 |
147 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 | ||
O1 | 0.49901 (9) | 0.3345 (2) | 0.06274 (13) | 0.0936 (6) | |
O2 | 0.36311 (8) | 0.76088 (17) | 0.29079 (10) | 0.0607 (4) | |
O3 | 0.38384 (8) | 0.98008 (19) | 0.20739 (11) | 0.0740 (5) | |
N1 | 0.38935 (8) | 0.57120 (19) | 0.15299 (11) | 0.0504 (4) | |
C1 | 0.47836 (12) | 0.4333 (3) | 0.10849 (17) | 0.0664 (6) | |
H1 | 0.5132 | 0.4880 | 0.1609 | 0.080* | |
C2 | 0.40071 (11) | 0.4739 (2) | 0.08687 (14) | 0.0517 (5) | |
C3 | 0.34551 (12) | 0.4121 (3) | 0.00338 (15) | 0.0591 (6) | |
H3 | 0.3567 | 0.3458 | −0.0413 | 0.071* | |
C4 | 0.27550 (12) | 0.4505 (2) | −0.01135 (15) | 0.0594 (6) | |
H4 | 0.2381 | 0.4111 | −0.0667 | 0.071* | |
C5 | 0.25934 (10) | 0.5498 (2) | 0.05699 (15) | 0.0513 (5) | |
C6 | 0.18791 (11) | 0.5936 (3) | 0.04871 (18) | 0.0648 (6) | |
H6 | 0.1483 | 0.5557 | −0.0045 | 0.078* | |
C7 | 0.17674 (12) | 0.6905 (3) | 0.1177 (2) | 0.0730 (7) | |
H7 | 0.1294 | 0.7187 | 0.1111 | 0.088* | |
C8 | 0.23503 (13) | 0.7488 (3) | 0.19863 (18) | 0.0671 (6) | |
H8 | 0.2263 | 0.8141 | 0.2457 | 0.080* | |
C9 | 0.30466 (11) | 0.7102 (2) | 0.20868 (15) | 0.0528 (5) | |
C10 | 0.31877 (10) | 0.6083 (2) | 0.13869 (13) | 0.0468 (5) | |
C11 | 0.40329 (12) | 0.8948 (3) | 0.27912 (16) | 0.0572 (6) | |
C12 | 0.47099 (13) | 0.9152 (3) | 0.36568 (15) | 0.0743 (7) | |
H12A | 0.5071 | 0.8365 | 0.3619 | 0.111* | |
H12B | 0.4611 | 0.8929 | 0.4235 | 0.111* | |
H12C | 0.4888 | 1.0293 | 0.3678 | 0.111* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0852 (13) | 0.0961 (13) | 0.1035 (14) | 0.0277 (10) | 0.0395 (11) | −0.0138 (10) |
O2 | 0.0672 (10) | 0.0644 (9) | 0.0526 (9) | −0.0017 (7) | 0.0246 (8) | −0.0006 (7) |
O3 | 0.0743 (11) | 0.0739 (11) | 0.0673 (11) | −0.0068 (8) | 0.0186 (9) | 0.0131 (8) |
N1 | 0.0443 (10) | 0.0531 (10) | 0.0511 (10) | 0.0015 (7) | 0.0147 (8) | 0.0025 (8) |
C1 | 0.0580 (15) | 0.0665 (15) | 0.0733 (15) | 0.0114 (11) | 0.0225 (12) | 0.0016 (12) |
C2 | 0.0508 (13) | 0.0491 (11) | 0.0527 (12) | 0.0019 (9) | 0.0164 (10) | 0.0023 (9) |
C3 | 0.0634 (15) | 0.0534 (13) | 0.0559 (13) | 0.0000 (10) | 0.0168 (12) | −0.0042 (10) |
C4 | 0.0612 (15) | 0.0496 (12) | 0.0546 (13) | −0.0122 (10) | 0.0063 (11) | 0.0025 (10) |
C5 | 0.0454 (12) | 0.0460 (11) | 0.0579 (13) | −0.0049 (9) | 0.0135 (10) | 0.0122 (10) |
C6 | 0.0443 (13) | 0.0617 (14) | 0.0809 (16) | −0.0055 (10) | 0.0142 (12) | 0.0163 (12) |
C7 | 0.0474 (14) | 0.0717 (16) | 0.105 (2) | 0.0042 (11) | 0.0343 (15) | 0.0234 (14) |
C8 | 0.0661 (16) | 0.0646 (14) | 0.0817 (17) | 0.0057 (11) | 0.0403 (14) | 0.0078 (12) |
C9 | 0.0515 (13) | 0.0543 (12) | 0.0555 (13) | 0.0004 (10) | 0.0232 (11) | 0.0066 (10) |
C10 | 0.0414 (12) | 0.0456 (11) | 0.0517 (12) | −0.0006 (8) | 0.0154 (10) | 0.0095 (9) |
C11 | 0.0588 (14) | 0.0595 (14) | 0.0567 (14) | 0.0069 (11) | 0.0254 (12) | −0.0056 (11) |
C12 | 0.0698 (16) | 0.0783 (17) | 0.0658 (15) | −0.0018 (12) | 0.0147 (13) | −0.0051 (12) |
O1—C1 | 1.195 (2) | C5—C6 | 1.412 (3) |
O2—C11 | 1.367 (2) | C5—C10 | 1.414 (3) |
O2—C9 | 1.389 (2) | C6—C7 | 1.354 (3) |
O3—C11 | 1.191 (2) | C6—H6 | 0.9300 |
N1—C2 | 1.324 (2) | C7—C8 | 1.396 (3) |
N1—C10 | 1.362 (2) | C7—H7 | 0.9300 |
C1—C2 | 1.481 (3) | C8—C9 | 1.361 (3) |
C1—H1 | 0.9300 | C8—H8 | 0.9300 |
C2—C3 | 1.397 (3) | C9—C10 | 1.415 (3) |
C3—C4 | 1.352 (3) | C11—C12 | 1.478 (3) |
C3—H3 | 0.9300 | C12—H12A | 0.9600 |
C4—C5 | 1.403 (3) | C12—H12B | 0.9600 |
C4—H4 | 0.9300 | C12—H12C | 0.9600 |
C11—O2—C9 | 116.42 (15) | C6—C7—H7 | 119.4 |
C2—N1—C10 | 116.86 (16) | C8—C7—H7 | 119.4 |
O1—C1—C2 | 124.1 (2) | C9—C8—C7 | 120.0 (2) |
O1—C1—H1 | 118.0 | C9—C8—H8 | 120.0 |
C2—C1—H1 | 118.0 | C7—C8—H8 | 120.0 |
N1—C2—C3 | 124.25 (18) | C8—C9—O2 | 120.7 (2) |
N1—C2—C1 | 114.17 (18) | C8—C9—C10 | 120.7 (2) |
C3—C2—C1 | 121.6 (2) | O2—C9—C10 | 118.47 (17) |
C4—C3—C2 | 118.9 (2) | N1—C10—C5 | 122.84 (18) |
C4—C3—H3 | 120.6 | N1—C10—C9 | 118.31 (17) |
C2—C3—H3 | 120.6 | C5—C10—C9 | 118.86 (18) |
C3—C4—C5 | 119.94 (19) | O3—C11—O2 | 122.3 (2) |
C3—C4—H4 | 120.0 | O3—C11—C12 | 126.9 (2) |
C5—C4—H4 | 120.0 | O2—C11—C12 | 110.85 (19) |
C4—C5—C6 | 123.9 (2) | C11—C12—H12A | 109.5 |
C4—C5—C10 | 117.23 (18) | C11—C12—H12B | 109.5 |
C6—C5—C10 | 118.8 (2) | H12A—C12—H12B | 109.5 |
C7—C6—C5 | 120.5 (2) | C11—C12—H12C | 109.5 |
C7—C6—H6 | 119.8 | H12A—C12—H12C | 109.5 |
C5—C6—H6 | 119.8 | H12B—C12—H12C | 109.5 |
C6—C7—C8 | 121.2 (2) | ||
C10—N1—C2—C3 | 1.8 (3) | C11—O2—C9—C8 | −104.8 (2) |
C10—N1—C2—C1 | −177.92 (16) | C11—O2—C9—C10 | 79.2 (2) |
O1—C1—C2—N1 | 172.6 (2) | C2—N1—C10—C5 | −1.0 (3) |
O1—C1—C2—C3 | −7.2 (3) | C2—N1—C10—C9 | 179.17 (16) |
N1—C2—C3—C4 | −1.2 (3) | C4—C5—C10—N1 | −0.4 (3) |
C1—C2—C3—C4 | 178.58 (18) | C6—C5—C10—N1 | 179.49 (16) |
C2—C3—C4—C5 | −0.4 (3) | C4—C5—C10—C9 | 179.40 (16) |
C3—C4—C5—C6 | −178.78 (18) | C6—C5—C10—C9 | −0.7 (3) |
C3—C4—C5—C10 | 1.1 (3) | C8—C9—C10—N1 | −178.98 (17) |
C4—C5—C6—C7 | −179.8 (2) | O2—C9—C10—N1 | −2.9 (3) |
C10—C5—C6—C7 | 0.3 (3) | C8—C9—C10—C5 | 1.2 (3) |
C5—C6—C7—C8 | −0.3 (3) | O2—C9—C10—C5 | 177.26 (15) |
C6—C7—C8—C9 | 0.8 (3) | C9—O2—C11—O3 | 10.7 (3) |
C7—C8—C9—O2 | −177.19 (17) | C9—O2—C11—C12 | −169.42 (17) |
C7—C8—C9—C10 | −1.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O1i | 0.93 | 2.57 | 3.486 (3) | 168 |
C12—H12C···O1ii | 0.96 | 2.59 | 3.447 (3) | 149 |
Symmetry codes: (i) x−1/2, y+1/2, z; (ii) −x+1, y+1, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H9NO3 |
Mr | 215.20 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 19.743 (3), 7.863 (1), 14.771 (2) |
β (°) | 111.66 (2) |
V (Å3) | 2131.1 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.53 × 0.46 × 0.41 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.950, 0.961 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6309, 2315, 1225 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.134, 1.00 |
No. of reflections | 2315 |
No. of parameters | 147 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.15 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O1i | 0.93 | 2.57 | 3.486 (3) | 168 |
C12—H12C···O1ii | 0.96 | 2.59 | 3.447 (3) | 149 |
Symmetry codes: (i) x−1/2, y+1/2, z; (ii) −x+1, y+1, −z+1/2. |
The title compound, (I), is a derivative of pyridylaldehyde, which readily forms Schiff base compounds by condensation with amines.
In (I), all the bond lengths are within normal ranges (Allen et al., 1987). The dihedral angle between the plane of atoms O2/C11/O3 and the quinoline ring is 82.9 (2)° (Fig. 1). The conformation of the acetoxy group is desecribed by the torsion angle of −169.42 (17)° for C9—O2—C11—C12.
In the crystal structure, molecules are linked via weak intermolecular C—H···O hydrogen bonds to form a two-dimensional sheet perpendicular to the c axis (Table 1).