Acta Cryst. (2008). E64, o527 [ doi:10.1107/S1600536808002547 ]
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-HO hydrogen bonds.
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.
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).
Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./ci2556fig1thm.gif)
| 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. |
![[Figure 2]](./ci2556fig2thm.gif)
| Fig. 2. Crystal packing of the title compound, viwed down the a axis. Hydrogen bonds are shown as dashed lines. |
| C16H17FN2O4·H2O | F000 = 712 |
| Mr = 338.33 | Dx = 1.377 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 24 reflections |
| a = 10.096 (4) Å | θ = 4.5–7.4º |
| b = 14.699 (5) Å | µ = 0.11 mm−1 |
| c = 11.028 (6) Å | T = 291 (2) K |
| β = 94.26 (4)º | Block, yellow |
| V = 1632.0 (12) Å3 | 0.45 × 0.42 × 0.39 mm |
| Z = 4 |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.007 |
| Radiation source: fine-focus sealed tube | θmax = 25.4º |
| Monochromator: graphite | θmin = 2.3º |
| T = 291(2) K | h = −12→12 |
| ω/2θ scans | k = 0→17 |
| Absorption correction: none | l = −4→13 |
| 3157 measured reflections | 3 standard reflections |
| 3009 independent reflections | every 300 reflections |
| 1741 reflections with I > 2σ(I) | intensity decay: 0.8% |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.043 | H 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 reflections | Δρmax = 0.20 e Å−3 |
| 235 parameters | Δρmin = −0.19 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C16H17FN2O4·H2O | V = 1632.0 (12) Å3 |
| Mr = 338.33 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 10.096 (4) Å | µ = 0.11 mm−1 |
| b = 14.699 (5) Å | T = 291 (2) K |
| c = 11.028 (6) Å | 0.45 × 0.42 × 0.39 mm |
| β = 94.26 (4)º |
| Enraf–Nonius CAD-4 diffractometer | Rint = 0.007 |
| Absorption correction: none | 3 standard reflections |
| 3157 measured reflections | every 300 reflections |
| 3009 independent reflections | intensity decay: 0.8% |
| 1741 reflections with I > 2σ(I) |
| R[F2 > 2σ(F2)] = 0.043 | 235 parameters |
| wR(F2) = 0.125 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | Δρmax = 0.20 e Å−3 |
| 3009 reflections | Δρmin = −0.19 e Å−3 |
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 | ||
| F1 | 0.51891 (13) | 0.59935 (11) | 1.01305 (12) | 0.0667 (4) | |
| O1 | 0.07128 (14) | 0.68291 (10) | 1.03507 (12) | 0.0451 (4) | |
| O2 | 0.33328 (14) | 0.56826 (12) | 0.58213 (13) | 0.0519 (4) | |
| O3 | −0.04405 (16) | 0.62649 (11) | 0.41364 (13) | 0.0552 (5) | |
| O4 | 0.16963 (18) | 0.62837 (18) | 0.37733 (15) | 0.1007 (9) | |
| N1 | 0.3174 (3) | 0.65375 (16) | 1.14712 (18) | 0.0514 (5) | |
| H1N1 | 0.385 (3) | 0.6210 (17) | 1.184 (2) | 0.068 (9)* | |
| H2N1 | 0.248 (3) | 0.6504 (18) | 1.186 (2) | 0.071 (9)* | |
| N2 | 0.01966 (16) | 0.64366 (12) | 0.77689 (13) | 0.0374 (4) | |
| C1 | 0.3794 (2) | 0.59542 (15) | 0.83243 (19) | 0.0436 (5) | |
| H1 | 0.4507 | 0.5774 | 0.7894 | 0.052* | |
| C2 | 0.3970 (2) | 0.61005 (15) | 0.95442 (19) | 0.0433 (5) | |
| C3 | 0.2938 (2) | 0.63708 (14) | 1.02489 (17) | 0.0397 (5) | |
| C4 | 0.1693 (2) | 0.65127 (13) | 0.96495 (17) | 0.0352 (5) | |
| C5 | 0.1457 (2) | 0.63418 (13) | 0.83915 (17) | 0.0333 (5) | |
| C6 | 0.2533 (2) | 0.60753 (13) | 0.77155 (17) | 0.0358 (5) | |
| C7 | 0.0710 (3) | 0.78037 (18) | 1.0445 (3) | 0.0786 (9) | |
| H7A | 0.1564 | 0.8008 | 1.0778 | 0.118* | |
| H7B | 0.0041 | 0.7990 | 1.0968 | 0.118* | |
| H7C | 0.0523 | 0.8064 | 0.9653 | 0.118* | |
| C8 | 0.2389 (2) | 0.59719 (14) | 0.63888 (17) | 0.0378 (5) | |
| C9 | 0.1107 (2) | 0.62227 (14) | 0.58234 (17) | 0.0401 (5) | |
| C10 | 0.0092 (2) | 0.64129 (14) | 0.65419 (17) | 0.0397 (5) | |
| H10 | −0.0738 | 0.6536 | 0.6152 | 0.048* | |
| C11 | −0.1031 (2) | 0.65083 (17) | 0.83913 (18) | 0.0449 (6) | |
| H11 | −0.1233 | 0.7109 | 0.8716 | 0.054* | |
| C12 | −0.2192 (2) | 0.5947 (2) | 0.7935 (2) | 0.0723 (9) | |
| H12A | −0.2086 | 0.5554 | 0.7242 | 0.087* | |
| H12B | −0.3070 | 0.6208 | 0.7971 | 0.087* | |
| C13 | −0.1436 (2) | 0.5712 (2) | 0.9108 (2) | 0.0627 (7) | |
| H13A | −0.1857 | 0.5830 | 0.9854 | 0.075* | |
| H13B | −0.0873 | 0.5177 | 0.9126 | 0.075* | |
| C14 | 0.0853 (2) | 0.62535 (17) | 0.44863 (19) | 0.0508 (6) | |
| C15 | −0.0802 (3) | 0.6314 (2) | 0.28436 (19) | 0.0693 (8) | |
| H15A | −0.0528 | 0.5763 | 0.2449 | 0.083* | |
| H15B | −0.0360 | 0.6826 | 0.2493 | 0.083* | |
| C16 | −0.2257 (2) | 0.64228 (17) | 0.2653 (2) | 0.0589 (7) | |
| H16A | −0.2687 | 0.5904 | 0.2979 | 0.088* | |
| H16B | −0.2506 | 0.6471 | 0.1798 | 0.088* | |
| H16C | −0.2523 | 0.6964 | 0.3058 | 0.088* | |
| O1W | 0.5509 (2) | 0.44950 (16) | 0.65115 (16) | 0.0715 (6) | |
| H1W | 0.606 (3) | 0.446 (2) | 0.598 (3) | 0.091 (11)* | |
| H2W | 0.486 (3) | 0.488 (2) | 0.621 (3) | 0.097 (11)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| F1 | 0.0396 (8) | 0.1032 (12) | 0.0559 (8) | 0.0081 (7) | −0.0058 (6) | −0.0147 (8) |
| O1 | 0.0457 (9) | 0.0567 (10) | 0.0346 (7) | 0.0092 (8) | 0.0143 (6) | −0.0021 (7) |
| O2 | 0.0422 (9) | 0.0766 (11) | 0.0388 (8) | 0.0138 (8) | 0.0163 (7) | −0.0026 (7) |
| O3 | 0.0469 (10) | 0.0891 (13) | 0.0303 (8) | 0.0030 (9) | 0.0083 (7) | 0.0013 (7) |
| O4 | 0.0523 (12) | 0.215 (3) | 0.0373 (10) | 0.0254 (13) | 0.0193 (9) | 0.0150 (12) |
| N1 | 0.0482 (13) | 0.0683 (15) | 0.0378 (11) | 0.0021 (11) | 0.0036 (10) | −0.0036 (10) |
| N2 | 0.0332 (10) | 0.0504 (11) | 0.0298 (9) | 0.0072 (8) | 0.0109 (7) | 0.0037 (7) |
| C1 | 0.0340 (12) | 0.0527 (14) | 0.0451 (13) | 0.0016 (10) | 0.0109 (10) | −0.0051 (10) |
| C2 | 0.0337 (12) | 0.0528 (14) | 0.0428 (12) | 0.0019 (10) | −0.0008 (10) | −0.0034 (10) |
| C3 | 0.0449 (13) | 0.0402 (12) | 0.0344 (11) | −0.0043 (10) | 0.0063 (9) | 0.0002 (9) |
| C4 | 0.0364 (12) | 0.0368 (11) | 0.0340 (10) | 0.0013 (9) | 0.0121 (9) | 0.0001 (9) |
| C5 | 0.0331 (11) | 0.0336 (11) | 0.0341 (10) | 0.0011 (9) | 0.0075 (8) | 0.0031 (8) |
| C6 | 0.0337 (12) | 0.0373 (12) | 0.0373 (11) | −0.0026 (9) | 0.0085 (9) | −0.0001 (8) |
| C7 | 0.097 (2) | 0.0622 (18) | 0.0805 (19) | 0.0211 (17) | 0.0311 (17) | −0.0148 (15) |
| C8 | 0.0384 (12) | 0.0414 (12) | 0.0355 (11) | −0.0007 (10) | 0.0145 (9) | −0.0008 (9) |
| C9 | 0.0378 (12) | 0.0518 (14) | 0.0315 (11) | 0.0038 (10) | 0.0093 (9) | 0.0018 (9) |
| C10 | 0.0350 (12) | 0.0519 (14) | 0.0327 (10) | 0.0079 (10) | 0.0069 (9) | 0.0078 (9) |
| C11 | 0.0320 (12) | 0.0659 (15) | 0.0385 (11) | 0.0082 (11) | 0.0129 (9) | 0.0041 (10) |
| C12 | 0.0403 (15) | 0.130 (3) | 0.0480 (14) | −0.0086 (15) | 0.0124 (12) | 0.0057 (15) |
| C13 | 0.0492 (15) | 0.094 (2) | 0.0469 (13) | −0.0127 (14) | 0.0168 (11) | 0.0119 (13) |
| C14 | 0.0444 (14) | 0.0763 (17) | 0.0331 (11) | 0.0094 (12) | 0.0123 (10) | 0.0023 (11) |
| C15 | 0.0627 (18) | 0.114 (2) | 0.0311 (12) | 0.0122 (16) | 0.0048 (12) | −0.0030 (13) |
| C16 | 0.0602 (17) | 0.0649 (17) | 0.0508 (14) | 0.0107 (13) | −0.0012 (12) | −0.0041 (12) |
| O1W | 0.0600 (13) | 0.1157 (18) | 0.0396 (9) | 0.0301 (12) | 0.0077 (9) | −0.0035 (10) |
| F1—C2 | 1.356 (2) | C7—H7B | 0.96 |
| O1—C4 | 1.381 (2) | C7—H7C | 0.96 |
| O1—C7 | 1.436 (3) | C8—C9 | 1.442 (3) |
| O2—C8 | 1.252 (2) | C9—C10 | 1.371 (3) |
| O3—C14 | 1.334 (3) | C9—C14 | 1.479 (3) |
| O3—C15 | 1.447 (3) | C10—H10 | 0.93 |
| O4—C14 | 1.202 (3) | C11—C13 | 1.486 (3) |
| N1—C3 | 1.373 (3) | C11—C12 | 1.490 (3) |
| N1—H1N1 | 0.91 (3) | C11—H11 | 0.98 |
| N1—H2N1 | 0.85 (3) | C12—C13 | 1.492 (4) |
| N2—C10 | 1.350 (2) | C12—H12A | 0.97 |
| N2—C5 | 1.408 (3) | C12—H12B | 0.97 |
| N2—C11 | 1.465 (3) | C13—H13A | 0.97 |
| C1—C2 | 1.361 (3) | C13—H13B | 0.97 |
| C1—C6 | 1.405 (3) | C15—C16 | 1.477 (3) |
| C1—H1 | 0.9300 | C15—H15A | 0.97 |
| C2—C3 | 1.403 (3) | C15—H15B | 0.97 |
| C3—C4 | 1.391 (3) | C16—H16A | 0.96 |
| C4—C5 | 1.413 (3) | C16—H16B | 0.96 |
| C5—C6 | 1.418 (3) | C16—H16C | 0.96 |
| C6—C8 | 1.467 (3) | O1W—H1W | 0.84 (3) |
| C7—H7A | 0.96 | O1W—H2W | 0.91 (3) |
| C4—O1—C7 | 112.45 (17) | N2—C10—C9 | 125.34 (19) |
| C14—O3—C15 | 117.11 (18) | N2—C10—H10 | 117.3 |
| C3—N1—H1N1 | 114.2 (16) | C9—C10—H10 | 117.3 |
| C3—N1—H2N1 | 113.3 (18) | N2—C11—C13 | 117.9 (2) |
| H1N1—N1—H2N1 | 112 (2) | N2—C11—C12 | 118.3 (2) |
| C10—N2—C5 | 119.16 (17) | C13—C11—C12 | 60.20 (17) |
| C10—N2—C11 | 117.75 (17) | N2—C11—H11 | 116.3 |
| C5—N2—C11 | 123.00 (15) | C13—C11—H11 | 116.3 |
| C2—C1—C6 | 119.99 (19) | C12—C11—H11 | 116.3 |
| C2—C1—H1 | 120.0 | C11—C12—C13 | 59.79 (16) |
| C6—C1—H1 | 120.0 | C11—C12—H12A | 117.8 |
| F1—C2—C1 | 120.05 (19) | C13—C12—H12A | 117.8 |
| F1—C2—C3 | 117.01 (18) | C11—C12—H12B | 117.8 |
| C1—C2—C3 | 122.9 (2) | C13—C12—H12B | 117.8 |
| N1—C3—C4 | 121.6 (2) | H12A—C12—H12B | 114.9 |
| N1—C3—C2 | 120.8 (2) | C11—C13—C12 | 60.01 (16) |
| C4—C3—C2 | 117.47 (18) | C11—C13—H13A | 117.8 |
| O1—C4—C3 | 116.36 (17) | C12—C13—H13A | 117.8 |
| O1—C4—C5 | 122.29 (18) | C11—C13—H13B | 117.8 |
| C3—C4—C5 | 121.36 (18) | C12—C13—H13B | 117.8 |
| N2—C5—C4 | 122.81 (18) | H13A—C13—H13B | 114.9 |
| N2—C5—C6 | 118.12 (17) | O4—C14—O3 | 122.4 (2) |
| C4—C5—C6 | 119.06 (18) | O4—C14—C9 | 125.0 (2) |
| C1—C6—C5 | 119.07 (18) | O3—C14—C9 | 112.52 (18) |
| C1—C6—C8 | 118.85 (18) | O3—C15—C16 | 108.7 (2) |
| C5—C6—C8 | 121.99 (18) | O3—C15—H15A | 109.9 |
| O1—C7—H7A | 109.5 | C16—C15—H15A | 109.9 |
| O1—C7—H7B | 109.5 | O3—C15—H15B | 109.9 |
| H7A—C7—H7B | 109.5 | C16—C15—H15B | 109.9 |
| O1—C7—H7C | 109.5 | H15A—C15—H15B | 108.3 |
| H7A—C7—H7C | 109.5 | C15—C16—H16A | 109.5 |
| H7B—C7—H7C | 109.5 | C15—C16—H16B | 109.5 |
| O2—C8—C9 | 124.20 (18) | H16A—C16—H16B | 109.5 |
| O2—C8—C6 | 120.70 (19) | C15—C16—H16C | 109.5 |
| C9—C8—C6 | 115.09 (17) | H16A—C16—H16C | 109.5 |
| C10—C9—C8 | 119.22 (18) | H16B—C16—H16C | 109.5 |
| C10—C9—C14 | 119.2 (2) | H1W—O1W—H2W | 107 (3) |
| C8—C9—C14 | 121.54 (18) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N1···O1Wi | 0.91 (3) | 2.15 (3) | 2.930 (3) | 143 (2) |
| N1—H2N1···O4ii | 0.85 (3) | 2.33 (3) | 3.061 (3) | 144 (2) |
| O1W—H1W···O2iii | 0.84 (3) | 2.13 (3) | 2.916 (3) | 155 (3) |
| O1W—H2W···O2 | 0.91 (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. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N1···O1Wi | 0.91 (3) | 2.15 (3) | 2.930 (3) | 143 (2) |
| N1—H2N1···O4ii | 0.85 (3) | 2.33 (3) | 3.061 (3) | 144 (2) |
| O1W—H1W···O2iii | 0.84 (3) | 2.13 (3) | 2.916 (3) | 155 (3) |
| O1W—H2W···O2 | 0.91 (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. |
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.
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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.
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).