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Acta Crystallogr Sect E Struct Rep Online. Nov 1, 2011; 67(Pt 11): o2895.
Published online Oct 8, 2011. doi:  10.1107/S1600536811041006
PMCID: PMC3247312
6-Benzyl-6,7-dihydro-5H-pyrrolo­[3,4-b]pyridine-5,7-dione
Hong-Shun Sun,a* Long Jiang,b Hong Xu,c Xin-Hua Lu,a and Yu-Long Lic
aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People’s Republic of China
bR&D Center, Jiangsu Yabang Pharmaceutical Group, Changzhou 213200, People’s Republic of China
cDepartment of Chemical Engineering, Nanjing College of Chemical Technology, Nanjing 210048, People’s Republic of China
Correspondence e-mail: njutshs/at/126.com
Received September 26, 2011; Accepted October 5, 2011.
Abstract
In the title compound, C14H10N2O2, the dihedral angle between the heterocyclic ring system and the phenyl ring is 45.8 (5)°. Weak inter­molecular C—H(...)N hydrogen bonding is present in the crystal structure.
Related literature
The title compound is a key inter­mediate in the synthesis of the quinolone anti­biotic moxifloxacin [systematic name: 1-cyclo­propyl-7-[(1S,6S)-2,8-diaza­bicyclo­[4.3.0]non-8-yl]-6-fluoro-8-meth­oxy-4-oxo-quinoline-3-carb­oxy­lic acid], see: Petersen et al. (1993 [triangle]). For a related structure, see: Garduño-Beltrán et al. (2009 [triangle]).
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Object name is e-67-o2895-scheme1.jpg Object name is e-67-o2895-scheme1.jpg
Crystal data
  • C14H10N2O2
  • M r = 238.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-67-o2895-efi1.jpg
  • a = 11.8548 (6) Å
  • b = 12.3969 (8) Å
  • c = 8.1676 (4) Å
  • β = 107.45 (3)°
  • V = 1145.1 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 293 K
  • 0.20 × 0.10 × 0.10 mm
Data collection
  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.981, T max = 0.991
  • 2087 measured reflections
  • 2087 independent reflections
  • 1100 reflections with I > 2σ(I)
  • R int = 0.045
  • 3 standard reflections every 200 reflections intensity decay: 1%
Refinement
  • R[F 2 > 2σ(F 2)] = 0.058
  • wR(F 2) = 0.174
  • S = 1.00
  • 2087 reflections
  • 163 parameters
  • 12 restraints
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.13 e Å−3
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Table 1
Table 1
Hydrogen-bond geometry (Å, °)
Supplementary Material
Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811041006/xu5342sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811041006/xu5342Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536811041006/xu5342Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank the Center of Testing and Analysis, Nanjing University, for support.
supplementary crystallographic information
Comment
Moxifloxacin (Petersen et al., 1993) is used to treat a variety of bacterial infections. This medication belongs to a class of drugs called quinolone antibiotics. The title compound is a key intermediate to synthesize it. As part of our studies in this area, we report here its crystal structure.
In the title compound, all bond lengths and angles show normal values. The dihedral angle between the heterocycle and benzyl group is 45.8 (5)° (Fig.1), similar to that found in a related strcture (Garduño-Beltrán et al., 2009). There is a intermolecular C—H···N hydrogen bond (Table 1) in the crystal structure.
Experimental
Benzylamine (3.85 ml, 35.2 mmol) was added to a suspension of 2,3-pyridinedicarboxylic anhydride (5 g, 33.5 mmol) in acetic acid (50 ml), and the mixture was heated under reflux for 18 h. It was then cooled to room temperature, concentrated in vacuo and the residue was triturated with diethyl ether to afford the title compound as a white solid in 57% yield. Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of an acetone solution.
Refinement
All H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.97 Å and Uiso(H) = 1.2 Ueq(C).
Figures
Fig. 1.
Fig. 1.
The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 50% probability level.
Crystal data
C14H10N2O2F(000) = 496
Mr = 238.24Dx = 1.382 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 11.8548 (6) Åθ = 10–13°
b = 12.3969 (8) ŵ = 0.10 mm1
c = 8.1676 (4) ÅT = 293 K
β = 107.45 (3)°Block, colorless
V = 1145.1 (2) Å30.20 × 0.10 × 0.10 mm
Z = 4
Data collection
Enraf–Nonius CAD-4 diffractometer1100 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.045
graphiteθmax = 25.4°, θmin = 1.8°
ω/2θ scansh = −14→13
Absorption correction: ψ scan (North et al., 1968)k = 0→14
Tmin = 0.981, Tmax = 0.991l = 0→9
2087 measured reflections3 standard reflections every 200 reflections
2087 independent reflections intensity decay: 1%
Refinement
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.174H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.082P)2] where P = (Fo2 + 2Fc2)/3
2087 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.17 e Å3
12 restraintsΔρmin = −0.13 e Å3
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
N10.2267 (2)0.6223 (2)0.0923 (3)0.0602 (7)
O10.20765 (18)0.43903 (17)0.1329 (3)0.0753 (7)
C10.4977 (3)0.7166 (3)0.2368 (5)0.0896 (11)
H1A0.46400.78100.18710.108*
N2−0.0141 (2)0.74370 (19)0.2194 (3)0.0711 (7)
O20.19962 (18)0.80705 (17)0.0885 (3)0.0782 (7)
C20.6005 (3)0.7199 (3)0.3733 (5)0.0957 (12)
H2B0.63270.78610.41700.115*
C30.6539 (3)0.6287 (3)0.4429 (4)0.0763 (9)
H3A0.72420.63070.53240.092*
C40.6038 (3)0.5337 (3)0.3807 (5)0.0980 (13)
H4A0.63980.46980.42890.118*
C50.5005 (3)0.5297 (3)0.2473 (5)0.0919 (12)
H5A0.46810.46300.20660.110*
C60.4446 (2)0.6219 (2)0.1734 (3)0.0577 (8)
C70.3308 (3)0.6186 (3)0.0307 (4)0.0758 (10)
H7A0.32820.6793−0.04540.091*
H7B0.32820.5530−0.03510.091*
C80.1751 (2)0.5306 (2)0.1379 (3)0.0570 (8)
C90.0735 (2)0.5705 (2)0.1955 (3)0.0505 (6)
C10−0.0010 (2)0.5161 (2)0.2533 (3)0.0493 (7)
H10A0.00400.44150.26530.059*
C11−0.0833 (3)0.5716 (2)0.2939 (4)0.0655 (8)
H11A−0.13720.53420.33530.079*
C12−0.0940 (3)0.6819 (2)0.2785 (3)0.0633 (8)
H12A−0.15500.71640.30750.076*
C130.0710 (2)0.6813 (2)0.1768 (3)0.0504 (6)
C140.1696 (3)0.7163 (2)0.1142 (3)0.0581 (8)
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
N10.0490 (14)0.0711 (16)0.0568 (14)0.0019 (13)0.0100 (11)0.0026 (13)
O10.0755 (15)0.0661 (14)0.0803 (15)0.0207 (12)0.0173 (12)−0.0042 (11)
C10.063 (2)0.075 (2)0.118 (3)−0.0018 (18)0.007 (2)0.021 (2)
N20.0711 (18)0.0628 (14)0.0755 (17)0.0089 (11)0.0162 (13)−0.0014 (12)
O20.0702 (15)0.0627 (13)0.0928 (16)−0.0110 (11)0.0108 (12)0.0161 (11)
C20.067 (2)0.084 (3)0.120 (3)−0.014 (2)0.003 (2)−0.005 (2)
C30.0509 (18)0.101 (3)0.076 (2)−0.001 (2)0.0185 (16)0.001 (2)
C40.068 (2)0.079 (3)0.129 (3)0.009 (2)0.003 (2)0.014 (2)
C50.073 (3)0.072 (2)0.113 (3)−0.0044 (19)0.000 (2)−0.010 (2)
C60.0490 (16)0.071 (2)0.0572 (16)0.0014 (16)0.0227 (14)0.0005 (16)
C70.0562 (19)0.114 (3)0.0586 (18)−0.0033 (18)0.0195 (16)0.0010 (18)
C80.0532 (18)0.0573 (19)0.0503 (17)0.0024 (15)−0.0002 (13)−0.0016 (13)
C90.0483 (15)0.0511 (12)0.0446 (15)0.0002 (12)0.0027 (12)−0.0005 (12)
C100.0542 (17)0.0359 (12)0.0503 (15)0.0001 (10)0.0040 (12)0.0023 (11)
C110.0599 (18)0.0689 (14)0.0665 (19)0.0027 (14)0.0171 (15)0.0000 (16)
C120.0601 (19)0.0673 (15)0.0618 (18)0.0126 (14)0.0171 (14)−0.0092 (16)
C130.0525 (15)0.0481 (12)0.0442 (14)−0.0032 (12)0.0049 (12)0.0002 (12)
C140.0516 (18)0.060 (2)0.0516 (17)−0.0023 (15)−0.0014 (13)0.0026 (14)
Geometric parameters (Å, °)
N1—C141.385 (4)C4—H4A0.9300
N1—C81.394 (3)C5—C61.367 (4)
N1—C71.467 (4)C5—H5A0.9300
O1—C81.203 (3)C6—C71.496 (4)
C1—C61.359 (4)C7—H7A0.9700
C1—C21.384 (5)C7—H7B0.9700
C1—H1A0.9300C8—C91.503 (4)
N2—C131.395 (3)C9—C101.306 (3)
N2—C121.411 (4)C9—C131.382 (4)
O2—C141.217 (3)C10—C111.315 (4)
C2—C31.336 (4)C10—H10A0.9300
C2—H2B0.9300C11—C121.376 (4)
C3—C41.347 (4)C11—H11A0.9300
C3—H3A0.9300C12—H12A0.9300
C4—C51.374 (4)C13—C141.474 (4)
C14—N1—C8112.4 (2)N1—C7—H7B109.0
C14—N1—C7124.4 (3)C6—C7—H7B109.0
C8—N1—C7123.2 (3)H7A—C7—H7B107.8
C6—C1—C2121.9 (3)O1—C8—N1126.2 (3)
C6—C1—H1A119.1O1—C8—C9128.0 (3)
C2—C1—H1A119.1N1—C8—C9105.8 (2)
C13—N2—C12113.2 (2)C10—C9—C13124.0 (3)
C3—C2—C1120.5 (3)C10—C9—C8129.5 (3)
C3—C2—H2B119.7C13—C9—C8106.5 (3)
C1—C2—H2B119.7C9—C10—C11117.1 (3)
C2—C3—C4118.7 (3)C9—C10—H10A121.5
C2—C3—H3A120.7C11—C10—H10A121.5
C4—C3—H3A120.7C10—C11—C12123.4 (3)
C3—C4—C5121.2 (3)C10—C11—H11A118.3
C3—C4—H4A119.4C12—C11—H11A118.3
C5—C4—H4A119.4C11—C12—N2121.3 (3)
C6—C5—C4121.2 (3)C11—C12—H12A119.4
C6—C5—H5A119.4N2—C12—H12A119.4
C4—C5—H5A119.4C9—C13—N2121.1 (3)
C1—C6—C5116.5 (3)C9—C13—C14109.8 (3)
C1—C6—C7121.8 (3)N2—C13—C14129.1 (2)
C5—C6—C7121.7 (3)O2—C14—N1125.2 (3)
N1—C7—C6112.7 (2)O2—C14—C13129.4 (3)
N1—C7—H7A109.0N1—C14—C13105.4 (2)
C6—C7—H7A109.0
C6—C1—C2—C32.8 (6)C13—C9—C10—C110.7 (4)
C1—C2—C3—C4−1.9 (6)C8—C9—C10—C11−179.4 (2)
C2—C3—C4—C50.6 (6)C9—C10—C11—C12−0.1 (4)
C3—C4—C5—C6−0.3 (6)C10—C11—C12—N2−1.1 (4)
C2—C1—C6—C5−2.4 (5)C13—N2—C12—C111.4 (4)
C2—C1—C6—C7177.4 (3)C10—C9—C13—N2−0.2 (4)
C4—C5—C6—C11.1 (5)C8—C9—C13—N2179.9 (2)
C4—C5—C6—C7−178.7 (3)C10—C9—C13—C14178.1 (2)
C14—N1—C7—C691.4 (3)C8—C9—C13—C14−1.8 (3)
C8—N1—C7—C6−87.6 (3)C12—N2—C13—C9−0.8 (4)
C1—C6—C7—N1−88.5 (4)C12—N2—C13—C14−178.8 (2)
C5—C6—C7—N191.3 (4)C8—N1—C14—O2177.7 (3)
C14—N1—C8—O1−179.2 (3)C7—N1—C14—O2−1.4 (4)
C7—N1—C8—O1−0.1 (4)C8—N1—C14—C13−1.1 (3)
C14—N1—C8—C90.0 (3)C7—N1—C14—C13179.8 (2)
C7—N1—C8—C9179.2 (2)C9—C13—C14—O2−176.9 (3)
O1—C8—C9—C100.5 (5)N2—C13—C14—O21.2 (5)
N1—C8—C9—C10−178.7 (3)C9—C13—C14—N11.8 (3)
O1—C8—C9—C13−179.6 (3)N2—C13—C14—N1179.9 (2)
N1—C8—C9—C131.1 (3)
Hydrogen-bond geometry (Å, °)
D—H···AD—HH···AD···AD—H···A
C10—H10A···N2i0.932.463.386 (3)177
Symmetry codes: (i) −x, y−1/2, −z+1/2.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5342).
References
  • Enraf–Nonius (1994). CAD-4 EXPRESS Enraf–Nonius, Delft, The Netherlands.
  • Garduño-Beltrán, O., Román-Bravo, P., Medrano, F. & Tlahuext, H. (2009). Acta Cryst. E65, o2581. [PMC free article] [PubMed]
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Petersen, U., Krebs, A. & Schenke, T. (1993). Eur. Patent Appl. EP 92 122 058.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
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