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

Li, J.

doi:10.1107/S160053681100362X

organic compounds

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Volume 67| Part 3| March 2011| Page o588

doi:10.1107/S160053681100362X

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4-(2-Aminophenyl)-10-oxa-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione

Jian Li ^a ^*

^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 ); Hart et al. (2004 ). For related structures, see: Li (2010a ,b ); Goh et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₂N₂O₃
M_r = 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 ) T_min = 0.963, T_max = 0.980
5021 measured reflections
1131 independent reflections
827 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100362X/lh5200sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100362X/lh5200Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of (I), with displacement ellipsoide drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.

4-(2-Aminophenyl)-10-oxa-4-azatricyclo[5.2.1.0^2,6]dec-8-ene-3,5-dione top

Crystal data top

C₁₄H₁₂N₂O₃	F(000) = 536
M_r = 256.26	D_x = 1.398 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 975 reflections
a = 10.4457 (11) Å	θ = 3.1–20.1°
b = 8.8245 (9) Å	µ = 0.10 mm⁻¹
c = 13.2114 (15) Å	T = 298 K
V = 1217.8 (2) Å³	Block, pale yellow
Z = 4	0.38 × 0.33 × 0.20 mm

Data collection top

Bruker SMART CCD diffractometer	1131 independent reflections
Radiation source: fine-focus sealed tube	827 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −12→11
T_min = 0.963, T_max = 0.980	k = −10→10
5021 measured reflections	l = −15→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0348P)²] where P = (F_o² + 2F_c²)/3
1131 reflections	(Δ/σ)_max < 0.001
173 parameters	Δρ_max = 0.14 e Å⁻³
1 restraint	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₁₄H₁₂N₂O₃	V = 1217.8 (2) Å³
M_r = 256.26	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 10.4457 (11) Å	µ = 0.10 mm⁻¹
b = 8.8245 (9) Å	T = 298 K
c = 13.2114 (15) Å	0.38 × 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)
T_min = 0.963, T_max = 0.980	R_int = 0.061
5021 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.084	H-atom parameters constrained
S = 1.01	Δρ_max = 0.14 e Å⁻³
1131 reflections	Δρ_min = −0.12 e Å⁻³
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

	x	y	z	U_iso*/U_eq
N1	0.0406 (3)	0.1444 (3)	0.0863 (2)	0.0401 (7)
N2	0.2069 (3)	0.1868 (4)	0.2520 (3)	0.0729 (11)
H2A	0.2110	0.1054	0.2164	0.087*
H2B	0.2577	0.1992	0.3025	0.087*
O1	−0.0454 (3)	−0.0189 (3)	0.20351 (18)	0.0680 (9)
O2	0.1232 (3)	0.2521 (3)	−0.0577 (2)	0.0671 (9)
O3	0.2418 (2)	−0.1090 (3)	0.03190 (19)	0.0562 (7)
C1	−0.0025 (4)	0.0040 (4)	0.1192 (3)	0.0467 (9)
C2	0.0207 (4)	−0.1091 (4)	0.0363 (3)	0.0476 (9)
H2	−0.0560	−0.1684	0.0201	0.057*
C3	0.0677 (3)	−0.0159 (4)	−0.0536 (3)	0.0469 (10)
H3	0.0115	−0.0229	−0.1128	0.056*
C4	0.0818 (3)	0.1439 (5)	−0.0139 (3)	0.0462 (10)
C5	0.0363 (4)	0.2805 (4)	0.1474 (3)	0.0442 (9)
C6	0.1193 (4)	0.2968 (4)	0.2282 (3)	0.0490 (10)
C7	0.1108 (5)	0.4281 (5)	0.2857 (3)	0.0709 (14)
H7	0.1657	0.4417	0.3404	0.085*
C8	0.0224 (6)	0.5379 (5)	0.2631 (4)	0.0818 (16)
H8	0.0173	0.6247	0.3029	0.098*
C9	−0.0598 (5)	0.5204 (5)	0.1810 (4)	0.0783 (14)
H9	−0.1187	0.5958	0.1652	0.094*
C10	−0.0533 (4)	0.3914 (5)	0.1239 (3)	0.0588 (11)
H10	−0.1087	0.3780	0.0695	0.071*
C11	0.1408 (4)	−0.2123 (4)	0.0576 (3)	0.0555 (11)
H11	0.1455	−0.2562	0.1256	0.067*
C12	0.1452 (4)	−0.3243 (5)	−0.0286 (3)	0.0640 (12)
H12	0.1251	−0.4269	−0.0259	0.077*
C13	0.1827 (4)	−0.2477 (5)	−0.1075 (3)	0.0629 (13)
H13	0.1946	−0.2846	−0.1728	0.075*
C14	0.2030 (4)	−0.0868 (4)	−0.0717 (3)	0.0548 (11)
H14	0.2615	−0.0259	−0.1130	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0467 (17)	0.0387 (18)	0.0349 (15)	−0.0027 (15)	0.0028 (13)	0.0024 (14)
N2	0.076 (3)	0.068 (2)	0.075 (3)	−0.004 (2)	−0.025 (2)	0.004 (2)
O1	0.094 (2)	0.066 (2)	0.0437 (16)	−0.0215 (16)	0.0186 (16)	0.0025 (14)
O2	0.093 (2)	0.0526 (19)	0.0561 (17)	−0.0006 (16)	0.0217 (16)	0.0131 (14)
O3	0.0502 (17)	0.0539 (16)	0.0644 (17)	−0.0025 (15)	−0.0137 (14)	−0.0007 (13)
C1	0.051 (2)	0.049 (2)	0.040 (2)	−0.008 (2)	−0.0003 (18)	−0.0011 (17)
C2	0.052 (2)	0.048 (2)	0.0433 (19)	−0.009 (2)	0.0000 (18)	−0.0039 (19)
C3	0.051 (2)	0.051 (2)	0.038 (2)	0.005 (2)	−0.0063 (17)	0.0006 (18)
C4	0.047 (2)	0.050 (3)	0.042 (2)	0.006 (2)	0.0011 (18)	0.009 (2)
C5	0.046 (2)	0.042 (2)	0.045 (2)	0.002 (2)	0.0095 (18)	0.0005 (18)
C6	0.053 (3)	0.049 (2)	0.045 (2)	−0.004 (2)	0.0000 (19)	−0.0003 (19)
C7	0.086 (4)	0.065 (3)	0.062 (3)	−0.027 (3)	0.014 (2)	−0.019 (2)
C8	0.095 (4)	0.053 (3)	0.097 (4)	−0.012 (3)	0.049 (3)	−0.028 (3)
C9	0.068 (4)	0.051 (3)	0.115 (4)	0.016 (3)	0.027 (3)	0.003 (3)
C10	0.055 (3)	0.047 (2)	0.075 (3)	0.003 (2)	0.008 (2)	0.004 (2)
C11	0.067 (3)	0.050 (2)	0.050 (2)	−0.003 (2)	−0.006 (2)	0.0055 (18)
C12	0.076 (3)	0.046 (3)	0.070 (3)	0.005 (2)	0.001 (2)	−0.008 (2)
C13	0.069 (3)	0.061 (3)	0.059 (3)	0.014 (2)	0.002 (2)	−0.013 (2)
C14	0.056 (3)	0.061 (3)	0.047 (2)	0.006 (2)	0.0046 (19)	0.003 (2)

Geometric parameters (Å, º) top

N1—C1	1.388 (4)	C5—C6	1.383 (5)
N1—C4	1.392 (4)	C5—C10	1.390 (5)
N1—C5	1.447 (4)	C6—C7	1.388 (5)
N2—C6	1.370 (5)	C7—C8	1.372 (7)
N2—H2A	0.8600	C7—H7	0.9300
N2—H2B	0.8600	C8—C9	1.392 (7)
O1—C1	1.217 (4)	C8—H8	0.9300
O2—C4	1.198 (4)	C9—C10	1.367 (6)
O3—C11	1.434 (4)	C9—H9	0.9300
O3—C14	1.440 (4)	C10—H10	0.9300
C1—C2	1.502 (5)	C11—C12	1.508 (5)
C2—C3	1.525 (5)	C11—H11	0.9800
C2—C11	1.576 (5)	C12—C13	1.303 (6)
C2—H2	0.9800	C12—H12	0.9300
C3—C4	1.512 (5)	C13—C14	1.512 (5)
C3—C14	1.564 (5)	C13—H13	0.9300
C3—H3	0.9800	C14—H14	0.9800

C1—N1—C4	113.3 (3)	C8—C7—C6	120.9 (5)
C1—N1—C5	123.8 (3)	C8—C7—H7	119.5
C4—N1—C5	122.9 (3)	C6—C7—H7	119.5
C6—N2—H2A	120.0	C7—C8—C9	120.4 (4)
C6—N2—H2B	120.0	C7—C8—H8	119.8
H2A—N2—H2B	120.0	C9—C8—H8	119.8
C11—O3—C14	96.0 (3)	C10—C9—C8	119.5 (4)
O1—C1—N1	123.6 (3)	C10—C9—H9	120.3
O1—C1—C2	128.1 (4)	C8—C9—H9	120.3
N1—C1—C2	108.2 (3)	C9—C10—C5	119.8 (4)
C1—C2—C3	105.2 (3)	C9—C10—H10	120.1
C1—C2—C11	112.4 (3)	C5—C10—H10	120.1
C3—C2—C11	101.2 (3)	O3—C11—C12	102.5 (3)
C1—C2—H2	112.4	O3—C11—C2	100.2 (3)
C3—C2—H2	112.4	C12—C11—C2	105.5 (3)
C11—C2—H2	112.4	O3—C11—H11	115.6
C4—C3—C2	105.3 (3)	C12—C11—H11	115.6
C4—C3—C14	109.8 (3)	C2—C11—H11	115.6
C2—C3—C14	101.2 (3)	C13—C12—C11	105.9 (4)
C4—C3—H3	113.2	C13—C12—H12	127.1
C2—C3—H3	113.2	C11—C12—H12	127.1
C14—C3—H3	113.2	C12—C13—C14	106.1 (4)
O2—C4—N1	124.7 (4)	C12—C13—H13	126.9
O2—C4—C3	127.7 (4)	C14—C13—H13	126.9
N1—C4—C3	107.6 (3)	O3—C14—C13	102.1 (3)
C6—C5—C10	121.4 (3)	O3—C14—C3	99.4 (3)
C6—C5—N1	119.9 (3)	C13—C14—C3	107.3 (3)
C10—C5—N1	118.7 (3)	O3—C14—H14	115.4
N2—C6—C5	121.4 (3)	C13—C14—H14	115.4
N2—C6—C7	120.6 (4)	C3—C14—H14	115.4
C5—C6—C7	118.0 (4)

C4—N1—C1—O1	−178.2 (4)	C10—C5—C6—C7	0.0 (5)
C5—N1—C1—O1	−1.7 (5)	N1—C5—C6—C7	−179.1 (3)
C4—N1—C1—C2	4.9 (4)	N2—C6—C7—C8	−179.2 (4)
C5—N1—C1—C2	−178.6 (3)	C5—C6—C7—C8	0.1 (6)
O1—C1—C2—C3	176.8 (4)	C6—C7—C8—C9	−0.7 (7)
N1—C1—C2—C3	−6.4 (4)	C7—C8—C9—C10	1.1 (7)
O1—C1—C2—C11	−73.9 (5)	C8—C9—C10—C5	−0.9 (6)
N1—C1—C2—C11	102.8 (3)	C6—C5—C10—C9	0.4 (6)
C1—C2—C3—C4	5.6 (4)	N1—C5—C10—C9	179.5 (3)
C11—C2—C3—C4	−111.6 (3)	C14—O3—C11—C12	48.6 (3)
C1—C2—C3—C14	119.9 (3)	C14—O3—C11—C2	−59.9 (3)
C11—C2—C3—C14	2.7 (3)	C1—C2—C11—O3	−77.4 (3)
C1—N1—C4—O2	−179.7 (4)	C3—C2—C11—O3	34.3 (3)
C5—N1—C4—O2	3.7 (6)	C1—C2—C11—C12	176.5 (3)
C1—N1—C4—C3	−1.1 (4)	C3—C2—C11—C12	−71.8 (4)
C5—N1—C4—C3	−177.7 (3)	O3—C11—C12—C13	−31.7 (4)
C2—C3—C4—O2	175.5 (4)	C2—C11—C12—C13	72.7 (4)
C14—C3—C4—O2	67.3 (5)	C11—C12—C13—C14	0.3 (5)
C2—C3—C4—N1	−3.0 (4)	C11—O3—C14—C13	−48.3 (3)
C14—C3—C4—N1	−111.2 (3)	C11—O3—C14—C3	61.8 (3)
C1—N1—C5—C6	72.1 (4)	C12—C13—C14—O3	31.1 (4)
C4—N1—C5—C6	−111.7 (4)	C12—C13—C14—C3	−72.9 (4)
C1—N1—C5—C10	−107.0 (4)	C4—C3—C14—O3	72.1 (3)
C4—N1—C5—C10	69.2 (5)	C2—C3—C14—O3	−38.9 (3)
C10—C5—C6—N2	179.4 (3)	C4—C3—C14—C13	178.0 (3)
N1—C5—C6—N2	0.3 (5)	C2—C3—C14—C13	67.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, y, z+1/2; (ii) −x, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₂N₂O₃
M_r	256.26
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	298
a, b, c (Å)	10.4457 (11), 8.8245 (9), 13.2114 (15)
V (Å³)	1217.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.38 × 0.33 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.963, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	5021, 1131, 827
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.084, 1.01
No. of reflections	1131
No. of parameters	173
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	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+1/2, y, z+1/2; (ii) −x, −y, z−1/2.

Acknowledgements

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

References

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