organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

4-(2-Amino­phen­yl)-10-oxa-4-aza­tri­cyclo­[5.2.1.02,6]dec-8-ene-3,5-dione

aDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
*Correspondence e-mail: ljwfu@163.com

(Received 17 January 2011; accepted 28 January 2011; online 9 February 2011)

In the title compound, C14H12N2O3, the essentially planar pyrrole ring [maximum deviation = 0.037 (4) Å] and the benzene ring form a dihedral angle of 69.5 (2)°. In the crystal, inter­molecular N—H⋯O hydrogen bonds connect mol­ecules into chains along [001]. Additional stabilization is provided by weak inter­molecular C—H⋯O hydrogen bonds.

Related literature

For the pharmacological applications of 7-oxabicyclo­[2.2.1]hept-5-ene-2,3-dicarb­oxy­lic anhydride and its derivatives, see: Deng & Hu (2007[Deng, L. P. & Hu, Y. Z. (2007). J. Heterocycl. Chem. 44, 597-601.]); Hart et al. (2004[Hart, M. E., Chamberlin, A. R., Walkom, C., Sakoff, J. A. & McCluskey, A. (2004). Bioorg. Med. Chem. Lett. 14, 1969-1973.]). For related structures, see: Li (2010a[Li, J. (2010a). Acta Cryst. E66, o3238.],b[Li, J. (2010b). Acta Cryst. E66, o3327.]); Goh et al. (2008[Goh, Y. W., Pool, B. R. & White, J. M. (2008). J. Org. Chem. 73, 151-156.]).

[Scheme 1]

Experimental

Crystal data
  • C14H12N2O3

  • Mr = 256.26

  • Orthorhombic, P c a 21

  • a = 10.4457 (11) Å

  • b = 8.8245 (9) Å

  • c = 13.2114 (15) Å

  • V = 1217.8 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 298 K

  • 0.38 × 0.33 × 0.20 mm

Data collection
  • Bruker SMART CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 1997[Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.963, Tmax = 0.980

  • 5021 measured reflections

  • 1131 independent reflections

  • 827 reflections with I > 2σ(I)

  • Rint = 0.061

Refinement
  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.084

  • S = 1.01

  • 1131 reflections

  • 173 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.14 e Å−3

  • Δρmin = −0.12 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2B⋯O2i 0.86 2.28 3.131 (5) 174
C3—H3⋯O1ii 0.98 2.48 3.232 (5) 133
Symmetry codes: (i) [-x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]; (ii) [-x, -y, z-{\script{1\over 2}}].

Data collection: SMART (Bruker, 1997[Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

7-Oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride has been widely employed in clinical practice, as it has low toxicity and is relatively easy to synthesize (Deng & Hu, 2007). Its derivatives are pharmacologically active (Hart et al., 2004). In this paper, the structure of the title compound, (I), is reported. The molecular structure of (I) is shown in Fig. 1. The bond lengths and bond angles are as expected and they are comparable to those in similar compounds (Li, 2010a,b; Goh, et al., 2008). The essentially planar pyrrole ring (maximum deviation = 0.037 (4)Å for atom C2) and the benzene ring form a dihedral angle of 69.5 (2) °. In the crystal, intermolecular N—H···O hydrogen bonds connect molecules into one-dimensional chains along [001]. Additional stabilization is provided by weak intermolecular C—H···O hydrogen bonds.

Related literature top

For the pharmacological applications of 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride and its derivatives, see: Deng & Hu (2007); Hart et al. (2004). For related structures, see: Li (2010a,b); Goh et al. (2008).

Experimental top

A mixture of exo-7-oxa-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride (0.332 g, 2 mmol) and benzene-1,2-diamine (0.216 g, 2 mmol) in methanol (5 ml) was stirred for 5 h at room temperature, and then refluxed for 1 h. After cooling the precipitate was filtered and dried, the title compound was obtained. The crude product of 20 mg was dissolved in methanol of 10 ml. The solution was filtered to remove impurities, and then the filtrate was left for crystallization at room temperature. The single-crystal suitable for X-ray determination was obtained by evaporation of a methanol solution of the title compound after 5 days.

Refinement top

In the absence of significant anomalous dispersion effects the Friedel pairs were merged. H atoms were initially located in difference maps and then refined in a riding-model approximation with C—H = 0.93–0.98 Å, N—H = 0.86Å and Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoide drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.
4-(2-Aminophenyl)-10-oxa-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione top
Crystal data top
C14H12N2O3F(000) = 536
Mr = 256.26Dx = 1.398 Mg m3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 975 reflections
a = 10.4457 (11) Åθ = 3.1–20.1°
b = 8.8245 (9) ŵ = 0.10 mm1
c = 13.2114 (15) ÅT = 298 K
V = 1217.8 (2) Å3Block, pale yellow
Z = 40.38 × 0.33 × 0.20 mm
Data collection top
Bruker SMART CCD
diffractometer
1131 independent reflections
Radiation source: fine-focus sealed tube827 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.061
ϕ and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 1211
Tmin = 0.963, Tmax = 0.980k = 1010
5021 measured reflectionsl = 1512
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0348P)2]
where P = (Fo2 + 2Fc2)/3
1131 reflections(Δ/σ)max < 0.001
173 parametersΔρmax = 0.14 e Å3
1 restraintΔρmin = 0.12 e Å3
Crystal data top
C14H12N2O3V = 1217.8 (2) Å3
Mr = 256.26Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 10.4457 (11) ŵ = 0.10 mm1
b = 8.8245 (9) ÅT = 298 K
c = 13.2114 (15) Å0.38 × 0.33 × 0.20 mm
Data collection top
Bruker SMART CCD
diffractometer
1131 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
827 reflections with I > 2σ(I)
Tmin = 0.963, Tmax = 0.980Rint = 0.061
5021 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0411 restraint
wR(F2) = 0.084H-atom parameters constrained
S = 1.01Δρmax = 0.14 e Å3
1131 reflectionsΔρmin = 0.12 e Å3
173 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
N10.0406 (3)0.1444 (3)0.0863 (2)0.0401 (7)
N20.2069 (3)0.1868 (4)0.2520 (3)0.0729 (11)
H2A0.21100.10540.21640.087*
H2B0.25770.19920.30250.087*
O10.0454 (3)0.0189 (3)0.20351 (18)0.0680 (9)
O20.1232 (3)0.2521 (3)0.0577 (2)0.0671 (9)
O30.2418 (2)0.1090 (3)0.03190 (19)0.0562 (7)
C10.0025 (4)0.0040 (4)0.1192 (3)0.0467 (9)
C20.0207 (4)0.1091 (4)0.0363 (3)0.0476 (9)
H20.05600.16840.02010.057*
C30.0677 (3)0.0159 (4)0.0536 (3)0.0469 (10)
H30.01150.02290.11280.056*
C40.0818 (3)0.1439 (5)0.0139 (3)0.0462 (10)
C50.0363 (4)0.2805 (4)0.1474 (3)0.0442 (9)
C60.1193 (4)0.2968 (4)0.2282 (3)0.0490 (10)
C70.1108 (5)0.4281 (5)0.2857 (3)0.0709 (14)
H70.16570.44170.34040.085*
C80.0224 (6)0.5379 (5)0.2631 (4)0.0818 (16)
H80.01730.62470.30290.098*
C90.0598 (5)0.5204 (5)0.1810 (4)0.0783 (14)
H90.11870.59580.16520.094*
C100.0533 (4)0.3914 (5)0.1239 (3)0.0588 (11)
H100.10870.37800.06950.071*
C110.1408 (4)0.2123 (4)0.0576 (3)0.0555 (11)
H110.14550.25620.12560.067*
C120.1452 (4)0.3243 (5)0.0286 (3)0.0640 (12)
H120.12510.42690.02590.077*
C130.1827 (4)0.2477 (5)0.1075 (3)0.0629 (13)
H130.19460.28460.17280.075*
C140.2030 (4)0.0868 (4)0.0717 (3)0.0548 (11)
H140.26150.02590.11300.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0467 (17)0.0387 (18)0.0349 (15)0.0027 (15)0.0028 (13)0.0024 (14)
N20.076 (3)0.068 (2)0.075 (3)0.004 (2)0.025 (2)0.004 (2)
O10.094 (2)0.066 (2)0.0437 (16)0.0215 (16)0.0186 (16)0.0025 (14)
O20.093 (2)0.0526 (19)0.0561 (17)0.0006 (16)0.0217 (16)0.0131 (14)
O30.0502 (17)0.0539 (16)0.0644 (17)0.0025 (15)0.0137 (14)0.0007 (13)
C10.051 (2)0.049 (2)0.040 (2)0.008 (2)0.0003 (18)0.0011 (17)
C20.052 (2)0.048 (2)0.0433 (19)0.009 (2)0.0000 (18)0.0039 (19)
C30.051 (2)0.051 (2)0.038 (2)0.005 (2)0.0063 (17)0.0006 (18)
C40.047 (2)0.050 (3)0.042 (2)0.006 (2)0.0011 (18)0.009 (2)
C50.046 (2)0.042 (2)0.045 (2)0.002 (2)0.0095 (18)0.0005 (18)
C60.053 (3)0.049 (2)0.045 (2)0.004 (2)0.0000 (19)0.0003 (19)
C70.086 (4)0.065 (3)0.062 (3)0.027 (3)0.014 (2)0.019 (2)
C80.095 (4)0.053 (3)0.097 (4)0.012 (3)0.049 (3)0.028 (3)
C90.068 (4)0.051 (3)0.115 (4)0.016 (3)0.027 (3)0.003 (3)
C100.055 (3)0.047 (2)0.075 (3)0.003 (2)0.008 (2)0.004 (2)
C110.067 (3)0.050 (2)0.050 (2)0.003 (2)0.006 (2)0.0055 (18)
C120.076 (3)0.046 (3)0.070 (3)0.005 (2)0.001 (2)0.008 (2)
C130.069 (3)0.061 (3)0.059 (3)0.014 (2)0.002 (2)0.013 (2)
C140.056 (3)0.061 (3)0.047 (2)0.006 (2)0.0046 (19)0.003 (2)
Geometric parameters (Å, º) top
N1—C11.388 (4)C5—C61.383 (5)
N1—C41.392 (4)C5—C101.390 (5)
N1—C51.447 (4)C6—C71.388 (5)
N2—C61.370 (5)C7—C81.372 (7)
N2—H2A0.8600C7—H70.9300
N2—H2B0.8600C8—C91.392 (7)
O1—C11.217 (4)C8—H80.9300
O2—C41.198 (4)C9—C101.367 (6)
O3—C111.434 (4)C9—H90.9300
O3—C141.440 (4)C10—H100.9300
C1—C21.502 (5)C11—C121.508 (5)
C2—C31.525 (5)C11—H110.9800
C2—C111.576 (5)C12—C131.303 (6)
C2—H20.9800C12—H120.9300
C3—C41.512 (5)C13—C141.512 (5)
C3—C141.564 (5)C13—H130.9300
C3—H30.9800C14—H140.9800
C1—N1—C4113.3 (3)C8—C7—C6120.9 (5)
C1—N1—C5123.8 (3)C8—C7—H7119.5
C4—N1—C5122.9 (3)C6—C7—H7119.5
C6—N2—H2A120.0C7—C8—C9120.4 (4)
C6—N2—H2B120.0C7—C8—H8119.8
H2A—N2—H2B120.0C9—C8—H8119.8
C11—O3—C1496.0 (3)C10—C9—C8119.5 (4)
O1—C1—N1123.6 (3)C10—C9—H9120.3
O1—C1—C2128.1 (4)C8—C9—H9120.3
N1—C1—C2108.2 (3)C9—C10—C5119.8 (4)
C1—C2—C3105.2 (3)C9—C10—H10120.1
C1—C2—C11112.4 (3)C5—C10—H10120.1
C3—C2—C11101.2 (3)O3—C11—C12102.5 (3)
C1—C2—H2112.4O3—C11—C2100.2 (3)
C3—C2—H2112.4C12—C11—C2105.5 (3)
C11—C2—H2112.4O3—C11—H11115.6
C4—C3—C2105.3 (3)C12—C11—H11115.6
C4—C3—C14109.8 (3)C2—C11—H11115.6
C2—C3—C14101.2 (3)C13—C12—C11105.9 (4)
C4—C3—H3113.2C13—C12—H12127.1
C2—C3—H3113.2C11—C12—H12127.1
C14—C3—H3113.2C12—C13—C14106.1 (4)
O2—C4—N1124.7 (4)C12—C13—H13126.9
O2—C4—C3127.7 (4)C14—C13—H13126.9
N1—C4—C3107.6 (3)O3—C14—C13102.1 (3)
C6—C5—C10121.4 (3)O3—C14—C399.4 (3)
C6—C5—N1119.9 (3)C13—C14—C3107.3 (3)
C10—C5—N1118.7 (3)O3—C14—H14115.4
N2—C6—C5121.4 (3)C13—C14—H14115.4
N2—C6—C7120.6 (4)C3—C14—H14115.4
C5—C6—C7118.0 (4)
C4—N1—C1—O1178.2 (4)C10—C5—C6—C70.0 (5)
C5—N1—C1—O11.7 (5)N1—C5—C6—C7179.1 (3)
C4—N1—C1—C24.9 (4)N2—C6—C7—C8179.2 (4)
C5—N1—C1—C2178.6 (3)C5—C6—C7—C80.1 (6)
O1—C1—C2—C3176.8 (4)C6—C7—C8—C90.7 (7)
N1—C1—C2—C36.4 (4)C7—C8—C9—C101.1 (7)
O1—C1—C2—C1173.9 (5)C8—C9—C10—C50.9 (6)
N1—C1—C2—C11102.8 (3)C6—C5—C10—C90.4 (6)
C1—C2—C3—C45.6 (4)N1—C5—C10—C9179.5 (3)
C11—C2—C3—C4111.6 (3)C14—O3—C11—C1248.6 (3)
C1—C2—C3—C14119.9 (3)C14—O3—C11—C259.9 (3)
C11—C2—C3—C142.7 (3)C1—C2—C11—O377.4 (3)
C1—N1—C4—O2179.7 (4)C3—C2—C11—O334.3 (3)
C5—N1—C4—O23.7 (6)C1—C2—C11—C12176.5 (3)
C1—N1—C4—C31.1 (4)C3—C2—C11—C1271.8 (4)
C5—N1—C4—C3177.7 (3)O3—C11—C12—C1331.7 (4)
C2—C3—C4—O2175.5 (4)C2—C11—C12—C1372.7 (4)
C14—C3—C4—O267.3 (5)C11—C12—C13—C140.3 (5)
C2—C3—C4—N13.0 (4)C11—O3—C14—C1348.3 (3)
C14—C3—C4—N1111.2 (3)C11—O3—C14—C361.8 (3)
C1—N1—C5—C672.1 (4)C12—C13—C14—O331.1 (4)
C4—N1—C5—C6111.7 (4)C12—C13—C14—C372.9 (4)
C1—N1—C5—C10107.0 (4)C4—C3—C14—O372.1 (3)
C4—N1—C5—C1069.2 (5)C2—C3—C14—O338.9 (3)
C10—C5—C6—N2179.4 (3)C4—C3—C14—C13178.0 (3)
N1—C5—C6—N20.3 (5)C2—C3—C14—C1367.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O2i0.862.283.131 (5)174
C3—H3···O1ii0.982.483.232 (5)133
Symmetry codes: (i) x+1/2, y, z+1/2; (ii) x, y, z1/2.

Experimental details

Crystal data
Chemical formulaC14H12N2O3
Mr256.26
Crystal system, space groupOrthorhombic, Pca21
Temperature (K)298
a, b, c (Å)10.4457 (11), 8.8245 (9), 13.2114 (15)
V3)1217.8 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.38 × 0.33 × 0.20
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.963, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
5021, 1131, 827
Rint0.061
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.084, 1.01
No. of reflections1131
No. of parameters173
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.12

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O2i0.862.283.131 (5)174
C3—H3···O1ii0.982.483.232 (5)133
Symmetry codes: (i) x+1/2, y, z+1/2; (ii) x, y, z1/2.
 

Acknowledgements

The author thanks the Shandong Provincial Natural Science Foundation, China (ZR2009BL027).

References

First citationBruker (1997). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDeng, L. P. & Hu, Y. Z. (2007). J. Heterocycl. Chem. 44, 597–601.  CrossRef CAS Google Scholar
First citationGoh, Y. W., Pool, B. R. & White, J. M. (2008). J. Org. Chem. 73, 151–156.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationHart, M. E., Chamberlin, A. R., Walkom, C., Sakoff, J. A. & McCluskey, A. (2004). Bioorg. Med. Chem. Lett. 14, 1969–1973.  Web of Science CrossRef PubMed CAS Google Scholar
First citationLi, J. (2010a). Acta Cryst. E66, o3238.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLi, J. (2010b). Acta Cryst. E66, o3327.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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