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In the structure of the title compound, C11H10N2O3, pairs of mol­ecules are linked into centrosymmetric dimers by N—H...O hydrogen bonds, which involve the cyclo­amino N—H and the keto C=O groups. In addition, the 4-amino group is involved in both intramolecular and intermolecular hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803004379/lh6030sup1.cif
Contains datablocks global, 3

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803004379/lh60303sup2.hkl
Contains datablock 3

CCDC reference: 209916

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.045
  • wR factor = 0.119
  • Data-to-parameter ratio = 12.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_731 Alert C Bond Calc 1.251(4), Rep 1.2509(19) .... 2.11 su-Ratio C2 -O21 1.555 1.555 PLAT_731 Alert C Bond Calc 1.445(5), Rep 1.445(2) .... 2.50 su-Ratio C2 -C3 1.555 1.555 PLAT_731 Alert C Bond Calc 1.470(5), Rep 1.470(2) .... 2.50 su-Ratio C3 -C31 1.555 1.555 PLAT_731 Alert C Bond Calc 1.457(5), Rep 1.457(2) .... 2.50 su-Ratio C4 -C5 1.555 1.555 PLAT_731 Alert C Bond Calc 1.403(5), Rep 1.403(2) .... 2.50 su-Ratio C5 -C6 1.555 1.555 PLAT_731 Alert C Bond Calc 1.366(5), Rep 1.366(2) .... 2.50 su-Ratio C8 -C9 1.555 1.555 PLAT_731 Alert C Bond Calc 1.443(5), Rep 1.443(2) .... 2.50 su-Ratio O32 -C34 1.555 1.555
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
7 Alert Level C = Please check

Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1998) plot of the molecule of the title compound. Displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. PLUTON97 (Spek, 1997) packing diagram, showing the hydrogen bonds as dashed lines.
Methyl 4-amino-2-oxo-1,2-dihydroquinoline-3-carboxylate top
Crystal data top
C11H10N2O3F(000) = 456
Mr = 218.21Dx = 1.468 Mg m3
Monoclinic, P21/cMelting point: melting point as described K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 10.033 (2) ÅCell parameters from 25 reflections
b = 7.27 (2) Åθ = 14–15°
c = 13.538 (3) ŵ = 0.11 mm1
β = 90.64 (2)°T = 293 K
V = 987 (3) Å3Prism, colourless
Z = 40.40 × 0.30 × 0.20 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.010
Radiation source: fine-focus sealed tubeθmax = 26.0°, θmin = 2.0°
Graphite monochromatorh = 1212
non–profiled ω scansk = 08
1939 measured reflectionsl = 016
1939 independent reflections3 standard reflections every 200 reflections
1414 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045H 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 reflectionsΔρmax = 0.20 e Å3
158 parametersΔρmin = 0.13 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.030 (4)
Crystal data top
C11H10N2O3V = 987 (3) Å3
Mr = 218.21Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.033 (2) ŵ = 0.11 mm1
b = 7.27 (2) ÅT = 293 K
c = 13.538 (3) Å0.40 × 0.30 × 0.20 mm
β = 90.64 (2)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.010
1939 measured reflections3 standard reflections every 200 reflections
1939 independent reflections intensity decay: none
1414 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.119H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.20 e Å3
1939 reflectionsΔρmin = 0.13 e Å3
158 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
N10.99148 (14)0.4031 (2)0.12286 (10)0.0401 (4)
C20.85944 (16)0.4048 (2)0.09974 (11)0.0358 (4)
C30.76797 (16)0.3685 (2)0.17911 (11)0.0355 (4)
C40.81480 (16)0.3533 (2)0.27646 (11)0.0368 (4)
C50.95738 (16)0.3666 (2)0.29668 (11)0.0356 (4)
C61.01406 (19)0.3619 (3)0.39185 (13)0.0469 (5)
C71.14979 (19)0.3714 (3)0.40644 (14)0.0515 (5)
C81.23311 (19)0.3833 (3)0.32573 (14)0.0505 (5)
C91.18106 (17)0.3905 (3)0.23214 (13)0.0457 (5)
C101.04329 (16)0.3856 (2)0.21718 (11)0.0354 (4)
O210.82627 (11)0.43656 (19)0.01204 (8)0.0459 (4)
C310.62522 (18)0.3416 (3)0.15816 (13)0.0437 (4)
O320.59773 (12)0.2855 (2)0.06646 (9)0.0569 (4)
O330.53779 (13)0.3601 (3)0.21788 (10)0.0750 (6)
C340.4585 (2)0.2577 (4)0.04310 (17)0.0766 (8)
N410.73308 (17)0.3251 (3)0.35292 (12)0.0523 (5)
H11.046 (2)0.439 (3)0.0734 (16)0.062 (6)*
H60.95870.35230.44620.056*
H71.18550.36980.47010.062*
H81.32500.38640.33530.061*
H91.23750.39860.17830.055*
H34A0.42010.17640.09090.115*
H34B0.44980.20450.02160.115*
H34C0.41290.37380.04440.115*
H4110.763 (2)0.282 (3)0.4097 (17)0.063 (6)*
H4120.641 (2)0.307 (3)0.3327 (15)0.062 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0362 (8)0.0614 (10)0.0229 (7)0.0063 (7)0.0040 (6)0.0035 (6)
C20.0379 (8)0.0465 (10)0.0229 (8)0.0051 (7)0.0019 (6)0.0008 (7)
C30.0367 (9)0.0458 (10)0.0242 (8)0.0002 (7)0.0026 (7)0.0015 (7)
C40.0406 (9)0.0453 (10)0.0246 (8)0.0012 (7)0.0059 (7)0.0005 (7)
C50.0424 (9)0.0405 (9)0.0239 (8)0.0021 (7)0.0012 (7)0.0014 (7)
C60.0532 (11)0.0616 (12)0.0259 (8)0.0012 (9)0.0000 (7)0.0047 (8)
C70.0541 (11)0.0661 (13)0.0341 (10)0.0045 (10)0.0125 (8)0.0060 (9)
C80.0429 (10)0.0606 (13)0.0477 (11)0.0033 (9)0.0075 (8)0.0067 (9)
C90.0411 (10)0.0591 (12)0.0369 (10)0.0042 (8)0.0031 (8)0.0042 (8)
C100.0397 (9)0.0409 (10)0.0256 (8)0.0023 (7)0.0002 (7)0.0007 (7)
O210.0431 (7)0.0760 (9)0.0186 (6)0.0096 (6)0.0007 (5)0.0037 (6)
C310.0380 (9)0.0608 (12)0.0323 (9)0.0013 (8)0.0034 (7)0.0053 (8)
O320.0360 (7)0.0973 (11)0.0374 (7)0.0081 (7)0.0028 (5)0.0086 (7)
O330.0387 (7)0.1438 (16)0.0426 (8)0.0003 (8)0.0107 (6)0.0056 (9)
C340.0411 (11)0.129 (2)0.0597 (14)0.0146 (13)0.0084 (10)0.0109 (14)
N410.0442 (9)0.0898 (13)0.0230 (8)0.0003 (9)0.0080 (7)0.0091 (8)
Geometric parameters (Å, º) top
N1—C21.358 (2)C7—H70.9300
N1—C101.379 (2)C8—C91.366 (2)
N1—H10.91 (2)C8—H80.9300
C2—O211.2509 (19)C9—C101.395 (2)
C2—C31.445 (2)C9—H90.9300
C3—C41.398 (2)C31—O331.207 (2)
C3—C311.470 (2)C31—O321.332 (2)
C4—N411.343 (2)O32—C341.443 (2)
C4—C51.457 (2)C34—H34A0.9600
C5—C101.393 (2)C34—H34B0.9600
C5—C61.403 (2)C34—H34C0.9600
C6—C71.375 (3)N41—H4110.88 (2)
C6—H60.9300N41—H4120.96 (2)
C7—C81.386 (3)
C2—N1—C10124.81 (15)C9—C8—H8119.8
C2—N1—H1114.7 (13)C7—C8—H8119.8
C10—N1—H1119.2 (13)C8—C9—C10120.10 (17)
O21—C2—N1117.97 (14)C8—C9—H9120.0
O21—C2—C3125.10 (15)C10—C9—H9120.0
N1—C2—C3116.93 (14)N1—C10—C5119.63 (15)
C4—C3—C2120.37 (15)N1—C10—C9119.64 (15)
C4—C3—C31119.19 (15)C5—C10—C9120.72 (15)
C2—C3—C31120.41 (14)O33—C31—O32120.92 (16)
N41—C4—C3122.46 (16)O33—C31—C3124.72 (17)
N41—C4—C5118.15 (15)O32—C31—C3114.30 (15)
C3—C4—C5119.39 (14)C31—O32—C34115.89 (15)
C10—C5—C6117.63 (16)O32—C34—H34A109.5
C10—C5—C4118.43 (14)O32—C34—H34B109.5
C6—C5—C4123.93 (15)H34A—C34—H34B109.5
C7—C6—C5121.41 (17)O32—C34—H34C109.5
C7—C6—H6119.3H34A—C34—H34C109.5
C5—C6—H6119.3H34B—C34—H34C109.5
C6—C7—C8119.66 (17)C4—N41—H411121.4 (14)
C6—C7—H7120.2C4—N41—H412112.9 (12)
C8—C7—H7120.2H411—N41—H412121 (2)
C9—C8—C7120.40 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O21i0.91 (2)1.96 (2)2.848 (8)166 (2)
N41—H411···O21ii0.88 (2)2.20 (2)3.015 (9)154 (2)
N41—H412···O330.97 (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 formulaC11H10N2O3
Mr218.21
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)10.033 (2), 7.27 (2), 13.538 (3)
β (°) 90.64 (2)
V3)987 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.40 × 0.30 × 0.20
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1939, 1939, 1414
Rint0.010
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.119, 1.03
No. of reflections1939
No. of parameters158
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Selected geometric parameters (Å, º) top
N1—C21.358 (2)C5—C61.403 (2)
N1—C101.379 (2)C6—C71.375 (3)
C2—O211.2509 (19)C7—C81.386 (3)
C2—C31.445 (2)C8—C91.366 (2)
C3—C41.398 (2)C9—C101.395 (2)
C3—C311.470 (2)C31—O331.207 (2)
C4—N411.343 (2)C31—O321.332 (2)
C4—C51.457 (2)O32—C341.443 (2)
C5—C101.393 (2)
C2—N1—C10124.81 (15)C6—C5—C4123.93 (15)
O21—C2—N1117.97 (14)C7—C6—C5121.41 (17)
O21—C2—C3125.10 (15)C6—C7—C8119.66 (17)
N1—C2—C3116.93 (14)C9—C8—C7120.40 (17)
C4—C3—C2120.37 (15)C8—C9—C10120.10 (17)
C4—C3—C31119.19 (15)N1—C10—C5119.63 (15)
C2—C3—C31120.41 (14)N1—C10—C9119.64 (15)
N41—C4—C3122.46 (16)C5—C10—C9120.72 (15)
N41—C4—C5118.15 (15)O33—C31—O32120.92 (16)
C3—C4—C5119.39 (14)O33—C31—C3124.72 (17)
C10—C5—C6117.63 (16)O32—C31—C3114.30 (15)
C10—C5—C4118.43 (14)C31—O32—C34115.89 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O21i0.91 (2)1.96 (2)2.848 (8)166 (2)
N41—H411···O21ii0.88 (2)2.20 (2)3.015 (9)154 (2)
N41—H412···O330.97 (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.
 

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