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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o527.
Published online 2008 January 30. doi:  10.1107/S1600536808002547
PMCID: PMC2960450

Ethyl 7-amino-1-cyclo­propyl-6-fluoro-8-meth­oxy-4-oxo-1,4-dihydro­quinoline-3-carboxyl­ate monohydrate

Abstract

In the title compound, C16H17FN2O4·H2O, the dihedral angle between the heterocyclic ring and the benzene ring is 5.77 (9)°, that between the heterocycle and the ethoxy­carbonyl plane is 15.5 (1)°, and that between the heterocyclic ring and the cyclopropane ring is 67.75 (13)°. In the crystal structure, mol­ecules are linked into a ribbon-like structure along the c axis by N—H(...)O and O—H(...)O hydrogen bonds.

Related literature

For general background, see: Fujita & Chiba (1998 [triangle]).

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Object name is e-64-0o527-scheme1.jpg

Experimental

Crystal data

  • C16H17FN2O4·H2O
  • M r = 338.33
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o527-efi1.jpg
  • a = 10.096 (4) Å
  • b = 14.699 (5) Å
  • c = 11.028 (6) Å
  • β = 94.26 (4)°
  • V = 1632.0 (12) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 291 (2) K
  • 0.45 × 0.42 × 0.39 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 3157 measured reflections
  • 3009 independent reflections
  • 1741 reflections with I > 2σ(I)
  • R int = 0.007
  • 3 standard reflections every 300 reflections intensity decay: 0.8%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.125
  • S = 1.04
  • 3009 reflections
  • 235 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: DIFRAC (Gabe & White, 1993 [triangle]); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808002547/ci2556sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808002547/ci2556Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

Quinolone antibacterials were found several decades ago, and some excellent antibacterials have been developed and used widely now (Fujita & Chiba, 1998). An interest in search of more potent antibacterial agents led us to design and synthesis a new type of quinoline derivatives. The title compound is one of the key intermediates and we report here its crystal structure.

The pyridinone ring is planar to within ±0.057 (2) Å (Fig. 1). The dihedral angle between the pyridine and benzene rings is 5.77 (9)°, and that between the pyridine and carboxylate plane is 15.5 (1)°. In the crystal structure, the molecules are linked into a ribbon like structure along the c axis (Fig. 2) by N—H···O and O—H···O hydrogen bonds (Table 1).

Experimental

Ethyl 7-azido-1-cyclopropyl-6-fluoro-8-methoxyl-4-oxo-1,4-dihydroquinoline-3- carboxylate (2 g, 5.8 mmol), 5% Pd/C (0.4 g) were suspended in methanol (20 ml) and the mixture was hydrogenated at 303 K for 6 h. The reaction mixture was then filtered and concentrated under vacuum. The residue obtained was purified by silica gel chromatography. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a acetyl acetate-chloroform (1.2:1 v/v) solution at room temperature.

Refinement

The water H atoms were located in a difference Fourier map and refined isotropically. The remaining H atoms were placed in the calculated positions [C—H = 0.93 (aromatic) and 0.96 Å (methyl)] and refined in the riding-model approximation, with Uiso(H) = 1.2Ueq(aromatic-C) and 1.5Ueq(methyl-C).

Figures

Fig. 1.
The molecular structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids drawn at the 30% probability level. The dashed line indicates a hydrogen bond.
Fig. 2.
Crystal packing of the title compound, viwed down the a axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C16H17FN2O4·H2OF000 = 712
Mr = 338.33Dx = 1.377 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 24 reflections
a = 10.096 (4) Åθ = 4.5–7.4º
b = 14.699 (5) ŵ = 0.11 mm1
c = 11.028 (6) ÅT = 291 (2) K
β = 94.26 (4)ºBlock, yellow
V = 1632.0 (12) Å30.45 × 0.42 × 0.39 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.007
Radiation source: fine-focus sealed tubeθmax = 25.4º
Monochromator: graphiteθmin = 2.3º
T = 291(2) Kh = −12→12
ω/2θ scansk = 0→17
Absorption correction: nonel = −4→13
3157 measured reflections3 standard reflections
3009 independent reflections every 300 reflections
1741 reflections with I > 2σ(I) intensity decay: 0.8%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.125  w = 1/[σ2(Fo2) + (0.0627P)2 + 0.1314P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
3009 reflectionsΔρmax = 0.20 e Å3
235 parametersΔρmin = −0.19 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
F10.51891 (13)0.59935 (11)1.01305 (12)0.0667 (4)
O10.07128 (14)0.68291 (10)1.03507 (12)0.0451 (4)
O20.33328 (14)0.56826 (12)0.58213 (13)0.0519 (4)
O3−0.04405 (16)0.62649 (11)0.41364 (13)0.0552 (5)
O40.16963 (18)0.62837 (18)0.37733 (15)0.1007 (9)
N10.3174 (3)0.65375 (16)1.14712 (18)0.0514 (5)
H1N10.385 (3)0.6210 (17)1.184 (2)0.068 (9)*
H2N10.248 (3)0.6504 (18)1.186 (2)0.071 (9)*
N20.01966 (16)0.64366 (12)0.77689 (13)0.0374 (4)
C10.3794 (2)0.59542 (15)0.83243 (19)0.0436 (5)
H10.45070.57740.78940.052*
C20.3970 (2)0.61005 (15)0.95442 (19)0.0433 (5)
C30.2938 (2)0.63708 (14)1.02489 (17)0.0397 (5)
C40.1693 (2)0.65127 (13)0.96495 (17)0.0352 (5)
C50.1457 (2)0.63418 (13)0.83915 (17)0.0333 (5)
C60.2533 (2)0.60753 (13)0.77155 (17)0.0358 (5)
C70.0710 (3)0.78037 (18)1.0445 (3)0.0786 (9)
H7A0.15640.80081.07780.118*
H7B0.00410.79901.09680.118*
H7C0.05230.80640.96530.118*
C80.2389 (2)0.59719 (14)0.63888 (17)0.0378 (5)
C90.1107 (2)0.62227 (14)0.58234 (17)0.0401 (5)
C100.0092 (2)0.64129 (14)0.65419 (17)0.0397 (5)
H10−0.07380.65360.61520.048*
C11−0.1031 (2)0.65083 (17)0.83913 (18)0.0449 (6)
H11−0.12330.71090.87160.054*
C12−0.2192 (2)0.5947 (2)0.7935 (2)0.0723 (9)
H12A−0.20860.55540.72420.087*
H12B−0.30700.62080.79710.087*
C13−0.1436 (2)0.5712 (2)0.9108 (2)0.0627 (7)
H13A−0.18570.58300.98540.075*
H13B−0.08730.51770.91260.075*
C140.0853 (2)0.62535 (17)0.44863 (19)0.0508 (6)
C15−0.0802 (3)0.6314 (2)0.28436 (19)0.0693 (8)
H15A−0.05280.57630.24490.083*
H15B−0.03600.68260.24930.083*
C16−0.2257 (2)0.64228 (17)0.2653 (2)0.0589 (7)
H16A−0.26870.59040.29790.088*
H16B−0.25060.64710.17980.088*
H16C−0.25230.69640.30580.088*
O1W0.5509 (2)0.44950 (16)0.65115 (16)0.0715 (6)
H1W0.606 (3)0.446 (2)0.598 (3)0.091 (11)*
H2W0.486 (3)0.488 (2)0.621 (3)0.097 (11)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.0396 (8)0.1032 (12)0.0559 (8)0.0081 (7)−0.0058 (6)−0.0147 (8)
O10.0457 (9)0.0567 (10)0.0346 (7)0.0092 (8)0.0143 (6)−0.0021 (7)
O20.0422 (9)0.0766 (11)0.0388 (8)0.0138 (8)0.0163 (7)−0.0026 (7)
O30.0469 (10)0.0891 (13)0.0303 (8)0.0030 (9)0.0083 (7)0.0013 (7)
O40.0523 (12)0.215 (3)0.0373 (10)0.0254 (13)0.0193 (9)0.0150 (12)
N10.0482 (13)0.0683 (15)0.0378 (11)0.0021 (11)0.0036 (10)−0.0036 (10)
N20.0332 (10)0.0504 (11)0.0298 (9)0.0072 (8)0.0109 (7)0.0037 (7)
C10.0340 (12)0.0527 (14)0.0451 (13)0.0016 (10)0.0109 (10)−0.0051 (10)
C20.0337 (12)0.0528 (14)0.0428 (12)0.0019 (10)−0.0008 (10)−0.0034 (10)
C30.0449 (13)0.0402 (12)0.0344 (11)−0.0043 (10)0.0063 (9)0.0002 (9)
C40.0364 (12)0.0368 (11)0.0340 (10)0.0013 (9)0.0121 (9)0.0001 (9)
C50.0331 (11)0.0336 (11)0.0341 (10)0.0011 (9)0.0075 (8)0.0031 (8)
C60.0337 (12)0.0373 (12)0.0373 (11)−0.0026 (9)0.0085 (9)−0.0001 (8)
C70.097 (2)0.0622 (18)0.0805 (19)0.0211 (17)0.0311 (17)−0.0148 (15)
C80.0384 (12)0.0414 (12)0.0355 (11)−0.0007 (10)0.0145 (9)−0.0008 (9)
C90.0378 (12)0.0518 (14)0.0315 (11)0.0038 (10)0.0093 (9)0.0018 (9)
C100.0350 (12)0.0519 (14)0.0327 (10)0.0079 (10)0.0069 (9)0.0078 (9)
C110.0320 (12)0.0659 (15)0.0385 (11)0.0082 (11)0.0129 (9)0.0041 (10)
C120.0403 (15)0.130 (3)0.0480 (14)−0.0086 (15)0.0124 (12)0.0057 (15)
C130.0492 (15)0.094 (2)0.0469 (13)−0.0127 (14)0.0168 (11)0.0119 (13)
C140.0444 (14)0.0763 (17)0.0331 (11)0.0094 (12)0.0123 (10)0.0023 (11)
C150.0627 (18)0.114 (2)0.0311 (12)0.0122 (16)0.0048 (12)−0.0030 (13)
C160.0602 (17)0.0649 (17)0.0508 (14)0.0107 (13)−0.0012 (12)−0.0041 (12)
O1W0.0600 (13)0.1157 (18)0.0396 (9)0.0301 (12)0.0077 (9)−0.0035 (10)

Geometric parameters (Å, °)

F1—C21.356 (2)C7—H7B0.96
O1—C41.381 (2)C7—H7C0.96
O1—C71.436 (3)C8—C91.442 (3)
O2—C81.252 (2)C9—C101.371 (3)
O3—C141.334 (3)C9—C141.479 (3)
O3—C151.447 (3)C10—H100.93
O4—C141.202 (3)C11—C131.486 (3)
N1—C31.373 (3)C11—C121.490 (3)
N1—H1N10.91 (3)C11—H110.98
N1—H2N10.85 (3)C12—C131.492 (4)
N2—C101.350 (2)C12—H12A0.97
N2—C51.408 (3)C12—H12B0.97
N2—C111.465 (3)C13—H13A0.97
C1—C21.361 (3)C13—H13B0.97
C1—C61.405 (3)C15—C161.477 (3)
C1—H10.9300C15—H15A0.97
C2—C31.403 (3)C15—H15B0.97
C3—C41.391 (3)C16—H16A0.96
C4—C51.413 (3)C16—H16B0.96
C5—C61.418 (3)C16—H16C0.96
C6—C81.467 (3)O1W—H1W0.84 (3)
C7—H7A0.96O1W—H2W0.91 (3)
C4—O1—C7112.45 (17)N2—C10—C9125.34 (19)
C14—O3—C15117.11 (18)N2—C10—H10117.3
C3—N1—H1N1114.2 (16)C9—C10—H10117.3
C3—N1—H2N1113.3 (18)N2—C11—C13117.9 (2)
H1N1—N1—H2N1112 (2)N2—C11—C12118.3 (2)
C10—N2—C5119.16 (17)C13—C11—C1260.20 (17)
C10—N2—C11117.75 (17)N2—C11—H11116.3
C5—N2—C11123.00 (15)C13—C11—H11116.3
C2—C1—C6119.99 (19)C12—C11—H11116.3
C2—C1—H1120.0C11—C12—C1359.79 (16)
C6—C1—H1120.0C11—C12—H12A117.8
F1—C2—C1120.05 (19)C13—C12—H12A117.8
F1—C2—C3117.01 (18)C11—C12—H12B117.8
C1—C2—C3122.9 (2)C13—C12—H12B117.8
N1—C3—C4121.6 (2)H12A—C12—H12B114.9
N1—C3—C2120.8 (2)C11—C13—C1260.01 (16)
C4—C3—C2117.47 (18)C11—C13—H13A117.8
O1—C4—C3116.36 (17)C12—C13—H13A117.8
O1—C4—C5122.29 (18)C11—C13—H13B117.8
C3—C4—C5121.36 (18)C12—C13—H13B117.8
N2—C5—C4122.81 (18)H13A—C13—H13B114.9
N2—C5—C6118.12 (17)O4—C14—O3122.4 (2)
C4—C5—C6119.06 (18)O4—C14—C9125.0 (2)
C1—C6—C5119.07 (18)O3—C14—C9112.52 (18)
C1—C6—C8118.85 (18)O3—C15—C16108.7 (2)
C5—C6—C8121.99 (18)O3—C15—H15A109.9
O1—C7—H7A109.5C16—C15—H15A109.9
O1—C7—H7B109.5O3—C15—H15B109.9
H7A—C7—H7B109.5C16—C15—H15B109.9
O1—C7—H7C109.5H15A—C15—H15B108.3
H7A—C7—H7C109.5C15—C16—H16A109.5
H7B—C7—H7C109.5C15—C16—H16B109.5
O2—C8—C9124.20 (18)H16A—C16—H16B109.5
O2—C8—C6120.70 (19)C15—C16—H16C109.5
C9—C8—C6115.09 (17)H16A—C16—H16C109.5
C10—C9—C8119.22 (18)H16B—C16—H16C109.5
C10—C9—C14119.2 (2)H1W—O1W—H2W107 (3)
C8—C9—C14121.54 (18)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N1···O1Wi0.91 (3)2.15 (3)2.930 (3)143 (2)
N1—H2N1···O4ii0.85 (3)2.33 (3)3.061 (3)144 (2)
O1W—H1W···O2iii0.84 (3)2.13 (3)2.916 (3)155 (3)
O1W—H2W···O20.91 (3)1.96 (3)2.864 (3)171 (3)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y, z+1; (iii) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI2556).

References

  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Fujita, M. & Chiba, K. (1998). Chem. Pharm. Bull.46, 631–638. [PubMed]
  • Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst.22, 384–387.
  • Gabe, E. J. & White, P. S. (1993). DIFRAC. American Crystallographic Association Pittsburgh Meeting Abstract PA 104.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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