Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803004379/lh6030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803004379/lh60303sup2.hkl |
CCDC reference: 209916
Preparation from (1): 2.32 g (0.01 mol) of (1) was refluxed for 1 h in 20 ml of methanol with 1.08 g (0.02 mol) sodium methylate. The reaction mixture was cooled to room temperature, 50 ml water was added and was acidified with the acetic acid to pH 4. The precipitate was filtered, washed with water and dried. Methyl 4-amino-2-oxo-1,2-dihydroquinoline-3-carboxylate, (3), was obtained (yield 2.03 g, 93%). Recrystallization from dimethylformamide gave colourless crystals (m.p. 554–556 K). 1H NMR (200 MHz, DMSO-d6): 3.72 (3H, s, Me), 7.04–7.23 (2H, m, 6,8-H), 7.53 (1H, t, 7-H), 8.07 (1H, d, 5-H), 8.37 (2H, s, NH2), 10.84 (1H, s, NH). Preparation from (2): a mixture of 2.37 g (0.01 mol) of (2) and 10 ml pyridine was heated under reflux for 30 min. Then 4.13 ml (0.05 mol) propylamine and 15 ml water were added and the resulting solution boiled for 4 h. After that, propylamine and most of the pyridine were removed in vacuo. The residue was worked up as in the previous experiment. The yield was 1.81 g (83%). The mixed test of the ester (3) samples obtained by the two methods did not give a depression of the melting-point temperature. Their 1H NMR spectra are identical.
H atoms bonded to N atoms were refined independently with isotropic displacement parameters and N—H bond lengths are in the range of 0.88 (2)–0.97 (2) Å. H atoms bonded to C atoms were included in calculated positions and refined as riding atoms. Calculated C—H bond lengths are in the range 0.93–0.96 Å.
Data collection: CAD-4 Software (Enraf Nonius, 1994); cell refinement: CAD-4 Software; data reduction: WinGX98 (Farrugia, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1998) and PLUTON97 (Spek, 1997); software used to prepare material for publication: WinGX (Farrugia, 1998).
C11H10N2O3 | F(000) = 456 |
Mr = 218.21 | Dx = 1.468 Mg m−3 |
Monoclinic, P21/c | Melting point: melting point as described K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.033 (2) Å | Cell parameters from 25 reflections |
b = 7.27 (2) Å | θ = 14–15° |
c = 13.538 (3) Å | µ = 0.11 mm−1 |
β = 90.64 (2)° | T = 293 K |
V = 987 (3) Å3 | Prism, colourless |
Z = 4 | 0.40 × 0.30 × 0.20 mm |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.010 |
Radiation source: fine-focus sealed tube | θmax = 26.0°, θmin = 2.0° |
Graphite monochromator | h = −12→12 |
non–profiled ω scans | k = 0→8 |
1939 measured reflections | l = 0→16 |
1939 independent reflections | 3 standard reflections every 200 reflections |
1414 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0622P)2 + 0.1214P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1939 reflections | Δρmax = 0.20 e Å−3 |
158 parameters | Δρmin = −0.13 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.030 (4) |
C11H10N2O3 | V = 987 (3) Å3 |
Mr = 218.21 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.033 (2) Å | µ = 0.11 mm−1 |
b = 7.27 (2) Å | T = 293 K |
c = 13.538 (3) Å | 0.40 × 0.30 × 0.20 mm |
β = 90.64 (2)° |
Enraf-Nonius CAD-4 diffractometer | Rint = 0.010 |
1939 measured reflections | 3 standard reflections every 200 reflections |
1939 independent reflections | intensity decay: none |
1414 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.119 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.20 e Å−3 |
1939 reflections | Δρmin = −0.13 e Å−3 |
158 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 | ||
N1 | 0.99148 (14) | 0.4031 (2) | 0.12286 (10) | 0.0401 (4) | |
C2 | 0.85944 (16) | 0.4048 (2) | 0.09974 (11) | 0.0358 (4) | |
C3 | 0.76797 (16) | 0.3685 (2) | 0.17911 (11) | 0.0355 (4) | |
C4 | 0.81480 (16) | 0.3533 (2) | 0.27646 (11) | 0.0368 (4) | |
C5 | 0.95738 (16) | 0.3666 (2) | 0.29668 (11) | 0.0356 (4) | |
C6 | 1.01406 (19) | 0.3619 (3) | 0.39185 (13) | 0.0469 (5) | |
C7 | 1.14979 (19) | 0.3714 (3) | 0.40644 (14) | 0.0515 (5) | |
C8 | 1.23311 (19) | 0.3833 (3) | 0.32573 (14) | 0.0505 (5) | |
C9 | 1.18106 (17) | 0.3905 (3) | 0.23214 (13) | 0.0457 (5) | |
C10 | 1.04329 (16) | 0.3856 (2) | 0.21718 (11) | 0.0354 (4) | |
O21 | 0.82627 (11) | 0.43656 (19) | 0.01204 (8) | 0.0459 (4) | |
C31 | 0.62522 (18) | 0.3416 (3) | 0.15816 (13) | 0.0437 (4) | |
O32 | 0.59773 (12) | 0.2855 (2) | 0.06646 (9) | 0.0569 (4) | |
O33 | 0.53779 (13) | 0.3601 (3) | 0.21788 (10) | 0.0750 (6) | |
C34 | 0.4585 (2) | 0.2577 (4) | 0.04310 (17) | 0.0766 (8) | |
N41 | 0.73308 (17) | 0.3251 (3) | 0.35292 (12) | 0.0523 (5) | |
H1 | 1.046 (2) | 0.439 (3) | 0.0734 (16) | 0.062 (6)* | |
H6 | 0.9587 | 0.3523 | 0.4462 | 0.056* | |
H7 | 1.1855 | 0.3698 | 0.4701 | 0.062* | |
H8 | 1.3250 | 0.3864 | 0.3353 | 0.061* | |
H9 | 1.2375 | 0.3986 | 0.1783 | 0.055* | |
H34A | 0.4201 | 0.1764 | 0.0909 | 0.115* | |
H34B | 0.4498 | 0.2045 | −0.0216 | 0.115* | |
H34C | 0.4129 | 0.3738 | 0.0444 | 0.115* | |
H411 | 0.763 (2) | 0.282 (3) | 0.4097 (17) | 0.063 (6)* | |
H412 | 0.641 (2) | 0.307 (3) | 0.3327 (15) | 0.062 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0362 (8) | 0.0614 (10) | 0.0229 (7) | −0.0063 (7) | 0.0040 (6) | 0.0035 (6) |
C2 | 0.0379 (8) | 0.0465 (10) | 0.0229 (8) | −0.0051 (7) | 0.0019 (6) | −0.0008 (7) |
C3 | 0.0367 (9) | 0.0458 (10) | 0.0242 (8) | 0.0002 (7) | 0.0026 (7) | 0.0015 (7) |
C4 | 0.0406 (9) | 0.0453 (10) | 0.0246 (8) | 0.0012 (7) | 0.0059 (7) | 0.0005 (7) |
C5 | 0.0424 (9) | 0.0405 (9) | 0.0239 (8) | −0.0021 (7) | 0.0012 (7) | 0.0014 (7) |
C6 | 0.0532 (11) | 0.0616 (12) | 0.0259 (8) | −0.0012 (9) | 0.0000 (7) | 0.0047 (8) |
C7 | 0.0541 (11) | 0.0661 (13) | 0.0341 (10) | −0.0045 (10) | −0.0125 (8) | 0.0060 (9) |
C8 | 0.0429 (10) | 0.0606 (13) | 0.0477 (11) | −0.0033 (9) | −0.0075 (8) | 0.0067 (9) |
C9 | 0.0411 (10) | 0.0591 (12) | 0.0369 (10) | −0.0042 (8) | 0.0031 (8) | 0.0042 (8) |
C10 | 0.0397 (9) | 0.0409 (10) | 0.0256 (8) | −0.0023 (7) | 0.0002 (7) | 0.0007 (7) |
O21 | 0.0431 (7) | 0.0760 (9) | 0.0186 (6) | −0.0096 (6) | −0.0007 (5) | 0.0037 (6) |
C31 | 0.0380 (9) | 0.0608 (12) | 0.0323 (9) | −0.0013 (8) | 0.0034 (7) | 0.0053 (8) |
O32 | 0.0360 (7) | 0.0973 (11) | 0.0374 (7) | −0.0081 (7) | −0.0028 (5) | −0.0086 (7) |
O33 | 0.0387 (7) | 0.1438 (16) | 0.0426 (8) | 0.0003 (8) | 0.0107 (6) | −0.0056 (9) |
C34 | 0.0411 (11) | 0.129 (2) | 0.0597 (14) | −0.0146 (13) | −0.0084 (10) | −0.0109 (14) |
N41 | 0.0442 (9) | 0.0898 (13) | 0.0230 (8) | −0.0003 (9) | 0.0080 (7) | 0.0091 (8) |
N1—C2 | 1.358 (2) | C7—H7 | 0.9300 |
N1—C10 | 1.379 (2) | C8—C9 | 1.366 (2) |
N1—H1 | 0.91 (2) | C8—H8 | 0.9300 |
C2—O21 | 1.2509 (19) | C9—C10 | 1.395 (2) |
C2—C3 | 1.445 (2) | C9—H9 | 0.9300 |
C3—C4 | 1.398 (2) | C31—O33 | 1.207 (2) |
C3—C31 | 1.470 (2) | C31—O32 | 1.332 (2) |
C4—N41 | 1.343 (2) | O32—C34 | 1.443 (2) |
C4—C5 | 1.457 (2) | C34—H34A | 0.9600 |
C5—C10 | 1.393 (2) | C34—H34B | 0.9600 |
C5—C6 | 1.403 (2) | C34—H34C | 0.9600 |
C6—C7 | 1.375 (3) | N41—H411 | 0.88 (2) |
C6—H6 | 0.9300 | N41—H412 | 0.96 (2) |
C7—C8 | 1.386 (3) | ||
C2—N1—C10 | 124.81 (15) | C9—C8—H8 | 119.8 |
C2—N1—H1 | 114.7 (13) | C7—C8—H8 | 119.8 |
C10—N1—H1 | 119.2 (13) | C8—C9—C10 | 120.10 (17) |
O21—C2—N1 | 117.97 (14) | C8—C9—H9 | 120.0 |
O21—C2—C3 | 125.10 (15) | C10—C9—H9 | 120.0 |
N1—C2—C3 | 116.93 (14) | N1—C10—C5 | 119.63 (15) |
C4—C3—C2 | 120.37 (15) | N1—C10—C9 | 119.64 (15) |
C4—C3—C31 | 119.19 (15) | C5—C10—C9 | 120.72 (15) |
C2—C3—C31 | 120.41 (14) | O33—C31—O32 | 120.92 (16) |
N41—C4—C3 | 122.46 (16) | O33—C31—C3 | 124.72 (17) |
N41—C4—C5 | 118.15 (15) | O32—C31—C3 | 114.30 (15) |
C3—C4—C5 | 119.39 (14) | C31—O32—C34 | 115.89 (15) |
C10—C5—C6 | 117.63 (16) | O32—C34—H34A | 109.5 |
C10—C5—C4 | 118.43 (14) | O32—C34—H34B | 109.5 |
C6—C5—C4 | 123.93 (15) | H34A—C34—H34B | 109.5 |
C7—C6—C5 | 121.41 (17) | O32—C34—H34C | 109.5 |
C7—C6—H6 | 119.3 | H34A—C34—H34C | 109.5 |
C5—C6—H6 | 119.3 | H34B—C34—H34C | 109.5 |
C6—C7—C8 | 119.66 (17) | C4—N41—H411 | 121.4 (14) |
C6—C7—H7 | 120.2 | C4—N41—H412 | 112.9 (12) |
C8—C7—H7 | 120.2 | H411—N41—H412 | 121 (2) |
C9—C8—C7 | 120.40 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O21i | 0.91 (2) | 1.96 (2) | 2.848 (8) | 166 (2) |
N41—H411···O21ii | 0.88 (2) | 2.20 (2) | 3.015 (9) | 154 (2) |
N41—H412···O33 | 0.97 (2) | 1.90 (2) | 2.677 (8) | 136 (2) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C11H10N2O3 |
Mr | 218.21 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.033 (2), 7.27 (2), 13.538 (3) |
β (°) | 90.64 (2) |
V (Å3) | 987 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1939, 1939, 1414 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.119, 1.03 |
No. of reflections | 1939 |
No. of parameters | 158 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.13 |
Computer programs: CAD-4 Software (Enraf Nonius, 1994), CAD-4 Software, WinGX98 (Farrugia, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1998) and PLUTON97 (Spek, 1997), WinGX (Farrugia, 1998).
N1—C2 | 1.358 (2) | C5—C6 | 1.403 (2) |
N1—C10 | 1.379 (2) | C6—C7 | 1.375 (3) |
C2—O21 | 1.2509 (19) | C7—C8 | 1.386 (3) |
C2—C3 | 1.445 (2) | C8—C9 | 1.366 (2) |
C3—C4 | 1.398 (2) | C9—C10 | 1.395 (2) |
C3—C31 | 1.470 (2) | C31—O33 | 1.207 (2) |
C4—N41 | 1.343 (2) | C31—O32 | 1.332 (2) |
C4—C5 | 1.457 (2) | O32—C34 | 1.443 (2) |
C5—C10 | 1.393 (2) | ||
C2—N1—C10 | 124.81 (15) | C6—C5—C4 | 123.93 (15) |
O21—C2—N1 | 117.97 (14) | C7—C6—C5 | 121.41 (17) |
O21—C2—C3 | 125.10 (15) | C6—C7—C8 | 119.66 (17) |
N1—C2—C3 | 116.93 (14) | C9—C8—C7 | 120.40 (17) |
C4—C3—C2 | 120.37 (15) | C8—C9—C10 | 120.10 (17) |
C4—C3—C31 | 119.19 (15) | N1—C10—C5 | 119.63 (15) |
C2—C3—C31 | 120.41 (14) | N1—C10—C9 | 119.64 (15) |
N41—C4—C3 | 122.46 (16) | C5—C10—C9 | 120.72 (15) |
N41—C4—C5 | 118.15 (15) | O33—C31—O32 | 120.92 (16) |
C3—C4—C5 | 119.39 (14) | O33—C31—C3 | 124.72 (17) |
C10—C5—C6 | 117.63 (16) | O32—C31—C3 | 114.30 (15) |
C10—C5—C4 | 118.43 (14) | C31—O32—C34 | 115.89 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O21i | 0.91 (2) | 1.96 (2) | 2.848 (8) | 166 (2) |
N41—H411···O21ii | 0.88 (2) | 2.20 (2) | 3.015 (9) | 154 (2) |
N41—H412···O33 | 0.97 (2) | 1.90 (2) | 2.677 (8) | 136 (2) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x, −y+1/2, z+1/2. |
An intial investigation of the structure of the title compound, (3), by 1H NMR spectroscopy suggested that this quinolone, in DMSO-d6 solution, was represented by two tautomers, namely the 4-amino-2-oxo, (3), and 4-imino-2-hydroxy, (4), forms in a 4:1 ratio. However, ethyl 4-amino-2-oxo-1,2-dihydroquinoline-3-carboxylate has been shown to have only the 1,2-dihydroform, (3) (Veronese et al., 1995).
We synthesized the title compound in two ways: with the help of intramolecular cyclization with the simultaneous re-esterification of 2-cyanomalonanilic acid ether, (1), as well as the reaction of methyl 4-chloro-2-oxo-1,2-dihydroquimoline-3-carboxylate, (2), with pyridine and the consequent degradation of the pyridinium group under the action of propylamine by the known method (Esteve & Gaozza, 1981; Gewald et al., 1991). According to our data, only the amidic tautomer, (3), is registered in the 1H NMR spectrum of the product obtained. The X-ray structure of the enolic form, (4), of the ester, (3), has not been determined.
The results of this present X-ray analysis show, that the 10-membered heterobicycle (N1/C1–C10) is planar within 0.077 (1) Å and atoms O21 and N41 show small displacements from its least-squares plane [0.218 (2) and −0.110 (3) Å, respectively]. The N1—H1···O21 intermolecular hydrogen bond [H1···O21i 1.96 (2) Å, N1···O21i 2.848 (8) Å and N1—H1···O21i 166 (2)°; symmetry code: (i) 2 − x, 1 − y, −z] links the molecules into centrosymmetric dimers. The previously investigated (Rybakov et al., 2001) crystal structure of 4-(4-ethoxyphenylamino)-2-oxo-1,2-dihydroguinoline forms the same type of hydrogen-bonded dimers. In addition, the 4-amino group is involved in intra- and intermolecular hydrogen bonding (see Table 2 and Fig. 2).