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Acta Cryst. (2007). E63, o4156    [ doi:10.1107/S1600536807046132 ]

N-(2-Aminophenyl)maleamic acid

N. F. Santos-Sánchez, R. Salas-Coronado, A. Peña-Hueso and A. Flores-Parra

Abstract top

The title compound [also called (Z)-3-(2-aminophenylcarbamoyl)propenoic acid], C10H10N2O3, is a non-planar amidated maleic acid derivative, with the mean planes through the 2-aminophenyl and maleamic acid groups inclined at an angle of 43.08 (10)°. Symmetry-related molecules are linked by intermolecular N-H...N hydrogen bonds, forming centrosymmetric amine-amide dimers. The dimers are linked by N-H...O and C-H...O hydrogen bonds and weak N-H...[pi] and [pi]-[pi] interactions [C-to-centroid distance 3.510 (3) Å] into a three-dimensional network.

Comment top

The title compound, (I), has been prepared by condensation from maleic anhydride and o-phenylenediamine as a intermediary for the synthesis of 1,2,3,4-tetrahydroquinoxalin-2-ones.

In the molecular structure of compound (I), the C2—C3 bond length of the maleamic moiety proves to have a clear double bond character and the bonds C1—C2 and C3—C4 are clearly single bonds, which confirms localized bonding, Table 1. The maleamic moiety is characterized by a rather short and almost linear O—H···O intramolecular hydrogen bond forming an S(7) ring (Bernstein et al., 1995), Figure 1. The C—O distances in the carboxylic acid group are consistent with the position of the carboxyl H atom deduced from difference maps. The title compound is non-planar with the mean planes through the 2-aminophenyl and maleamic acid groups being inclined against each other at an angle of 43.08 (10)°.

The crystal packing for (I) shows that the molecules are linked by two close to linear N—H···N hydrogen bonds (see Table 2 for geometric parameters and symmetry codes) to form centrosymmetric R22(10) dimers (Figure 2). These hydrogen bonds probably are the reason for the non-planarity of compound (I).

Adjacent dimers of (I) are linked by N—H···O and C—H···O hydrogen bonds and also by weaker N—H···π contacts and π···π stacking interactions. Amino atom N6 acts as a hydrogen-bond donor, via H61, to atom O2 in the molecule at (-x, y − 1/2, −z + 1/2), while atom C7 at (-x, y − 1/2, −z + 1/2), in turn, acts as donor to O2 at (x, y − 1, z). In this manner, a C(10) chain is formed (motif a, Figure 3.), running along the c axis. The arrangement of N6—H61···O2ii, N6ii—H61ii···O2iv, C7iii—H7iii···O4iv, C7—H7···O4iii interactions can be described by the graph-set notation R44(28). Aromatic carbon atom C7 acts as a hydrogen-bond donor, via H7, to O4 in the molecule at (-x + 1, y - 1/2, -z + 3/2), while C7 at (−x + 1, y - 1/2, −z + 3/2), in turn, acts as a donor to O4 at (x, y − 1, z). In this manner, a C(7) zigzag chain (motif b) is formed, running along the b axis, Figure 3. The geometry of the hydrogen bonding is given in Table 2. The amine hydrogen atom H62 is forming a N—H···π interaction with aromatic carbon C9 at (−x + 1, y − 1/2, -z + 3/2). These interactions are dominated by dispersion energies, Vaupel et al. (2006). Lastly, maleamic moieties do interact with the C5—C10 benzene ring (centroid Cg) at (x - 1, −y + 3/2, z − 1/2), the distance C1···Cg is 3.510 (3) Å and the gamma angle is 22.8°, Figure 4.

Related literature top

For related literature, see: Bernstein et al. (1995); Vaupel et al. (2006).

Experimental top

To a solution of o-phenylenediamine (9.2 mmol) in THF (20 ml) is added a solution of maleic anhydride (0.91 g, 9.3 mmol) in THF (20 ml). The suspension was stirred for 12 h at room temperature. The mixture was filtered and the solvent distilled off. The residue was precipitated with a mixture of acetone/hexane to give a yellow solid (1.87 g, 98%), which was washed with ethyl ether and recrystallized from THF to give yellow crystals suitable for single-crystal X-ray diffraction (m.p. 412–413 K). Rf (4:6:0.1, hexane: AcOEt: formic acid) 0.23. 1H NMR (300.13 MHz, DMSO-d6): δ 9.85 (s, 1H, CO2H), 8.04 (bs, 2H, NH2), 7.14 (bd, J = 7.9 Hz, 1H, H10), 6.97 (td, J = 7.9, 1.2 Hz, 1H, H8), 6.74 (bd, J = 7.9 Hz, 1H, H7), 6.61 (d, J = 12.2 Hz, 1H, H3), 6.56 (td, J = 7.9, 1.0 Hz, 1H, H9), 6.27 (d, J = 12.2 Hz, 1H, H2); 13C NMR (75.47 MHz, DMSO-d6): δ 167.5 (CO2), 165.0 (C4), 143.9 (C5), 134.5 (C3), 130.6 (C2), 127.8 (C8), 127.0 (C10), 122.4 (C6), 116.8 (C9), 116.5 (C7). MS [EI, m/z (%)]: 206 (100), 160 (64), 147 (99), 119 (36). HRMS calcd for [C10H10N2O3 + H]+ 207.0764, found 207.0769. F T–IR (KBr) (cm−1): 3388, 3308, 1706, 1308, 839.

Refinement top

All non-hydrogen atoms were refined anisotropically, C—H and amide hydrogen were placed in calculated positions, with distances C—H = 0.95 Å, N—H = 0.87 Å and O—H = 0.87 Å and Uiso(H) = 1.2 Ueq (C, N) or 1.5 Ueq (O). The H atoms of the amine group were refined but the N—H distances were restrained to 0.87 (2) Å [Uiso(H) = 1.2 Ueq(N)].

Computing details top

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. A view of (I), showing 30% probability displacement ellipsoids (H atoms are draw as small spheres of arbritary radii).
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded R22(10) dimer. Dashed lines indicate hydrogen bonds. Atoms marked with (i) are the at the symmetry related position (−x + 1, −y + 1, −z + 1).
[Figure 3] Fig. 3. The packing of (I), showing the R44(28) ring pattern. Dashed lines indicate hydrogen bonds. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. [Symmetry codes: (ii) -x, y − 1/2, −z + 1/2; (iii) −x + 1, y - 1/2, -z + 3/2; (iv) x, y − 1, z.]
[Figure 4] Fig. 4. Part of the crystal structure of (I), showing the formation weak N—H···π and π···π interactions. For clarity, all H atoms not involved in the motifs shown have been omitted [Symmetry codes: (iii) −x + 1, y − 1/2, −z + 3/2; (v) −1 + x, 3/2 − y, −1/2 + z.]
(Z)-3-(2-aminophenylcarbamoyl)propenoic acid top
Crystal data top
C10H10N2O3F000 = 432
Mr = 206.2Dx = 1.425 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2535 reflections
a = 7.3899 (2) Åθ = 1–29º
b = 12.2135 (3) ŵ = 0.11 mm−1
c = 12.2633 (3) ÅT = 294 K
β = 119.7260 (10)ºPrism, colourless
V = 961.19 (4) Å30.25 × 0.25 × 0.1 mm
Z = 4
Data collection top
Nonius KappaCCD area-detector
diffractometer		1155 reflections with I > 2.5σ(I)
Monochromator: graphiteRint = 0.039
Detector resolution: 9 pixels mm-1θmax = 28.6º
T = 291 Kθmin = 2.5º
φ and ω scansh = −9→9
Absorption correction: nonek = −16→16
4773 measured reflectionsl = −16→16
2418 independent reflections
Refinement top
Refinement on FSecondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.051  Method = Modified Sheldrick w = 1/[σ2(F2) + (0.04P)2],
where P = (max(Fo2,0) + 2Fc2)/3 (Sheldrick, 1997)
S = 1.01(Δ/σ)max = 0.0002
1155 reflectionsΔρmax = 0.17 e Å−3
142 parametersΔρmin = −0.17 e Å−3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C10H10N2O3V = 961.19 (4) Å3
Mr = 206.2Z = 4
Monoclinic, P21/cMo Kα
a = 7.3899 (2) ŵ = 0.11 mm−1
b = 12.2135 (3) ÅT = 294 K
c = 12.2633 (3) Å0.25 × 0.25 × 0.1 mm
β = 119.7260 (10)º
Data collection top
Nonius KappaCCD area-detector
diffractometer		2418 independent reflections
Absorption correction: none1155 reflections with I > 2.5σ(I)
4773 measured reflectionsRint = 0.039
Refinement top
R[F2 > 2σ(F2)] = 0.0412 restraints
wR(F2) = 0.051H atoms treated by a mixture of
independent and constrained refinement
S = 1.01Δρmax = 0.17 e Å−3
1155 reflectionsΔρmin = −0.17 e Å−3
142 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 > 2sigma(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
C10.0694 (3)0.9421 (2)0.2238 (2)0.0631
C20.1320 (3)0.82792 (19)0.21902 (19)0.0626
C30.2464 (3)0.75461 (18)0.30799 (19)0.0566
C40.3461 (3)0.76698 (16)0.44500 (18)0.0479
C50.5634 (3)0.67199 (14)0.64461 (16)0.0421
C60.5469 (3)0.57449 (15)0.69851 (16)0.0449
C70.6578 (3)0.56406 (18)0.82783 (18)0.057
C80.7808 (3)0.64865 (18)0.9029 (2)0.0633
C90.7967 (3)0.74467 (17)0.84874 (19)0.0575
C100.6885 (3)0.75622 (15)0.71998 (18)0.0491
H10.20940.94520.3920.1064*
H20.07820.80310.13710.0719*
H30.26630.68610.28180.0655*
H40.46460.62450.47050.0569*
H70.64560.49750.86450.0697*
H80.85450.64060.99150.0728*
H90.88290.80210.90080.0643*
H100.70230.82060.68380.0573*
H610.316 (3)0.5050 (17)0.5507 (16)0.0671*
H620.409 (3)0.4385 (16)0.6653 (18)0.0687*
N40.4533 (2)0.67995 (12)0.51109 (13)0.0474
N60.4266 (3)0.48726 (14)0.62196 (17)0.0557
O10.1358 (2)0.99089 (13)0.33127 (15)0.0797
O2−0.0414 (3)0.99077 (16)0.12712 (16)0.0937
O40.3304 (2)0.85106 (12)0.49678 (12)0.0711
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0556 (12)0.0661 (15)0.0542 (14)−0.0072 (11)0.0170 (11)0.0160 (12)
C20.0636 (12)0.0744 (16)0.0390 (12)−0.0143 (12)0.0172 (10)−0.0011 (11)
C30.0666 (13)0.0534 (13)0.0449 (12)−0.0047 (11)0.0240 (11)−0.0063 (10)
C40.0549 (11)0.0432 (11)0.0430 (11)−0.0034 (9)0.0222 (9)−0.0036 (9)
C50.0471 (10)0.0398 (10)0.0399 (10)0.0036 (8)0.0218 (9)−0.0006 (8)
C60.0513 (10)0.0395 (10)0.0478 (11)0.0024 (9)0.0276 (9)−0.0007 (8)
C70.0703 (13)0.0511 (12)0.0524 (12)0.0047 (11)0.0327 (11)0.0069 (10)
C80.0742 (14)0.0642 (15)0.0421 (11)0.0112 (12)0.0217 (10)0.0035 (11)
C90.0591 (12)0.0517 (13)0.0479 (13)0.0028 (10)0.0160 (10)−0.0073 (10)
C100.0542 (11)0.0399 (11)0.0499 (12)−0.0002 (9)0.0233 (10)−0.0017 (9)
N40.0635 (10)0.0367 (9)0.0416 (9)0.0011 (8)0.0257 (8)−0.0037 (7)
N60.0686 (11)0.0415 (10)0.0590 (12)−0.0063 (9)0.0331 (10)−0.0004 (8)
O10.0946 (12)0.0566 (10)0.0640 (11)0.0115 (8)0.0210 (9)0.0103 (8)
O20.0916 (12)0.0978 (14)0.0665 (11)0.0065 (10)0.0199 (10)0.0353 (10)
O40.0936 (11)0.0542 (9)0.0460 (9)0.0215 (8)0.0197 (8)−0.0042 (7)
Geometric parameters (Å, °) top
C1—C21.479 (3)C6—N61.407 (2)
C1—O11.301 (3)C7—C81.383 (3)
C1—O21.211 (2)C7—H70.954
C2—C31.339 (3)C8—C91.381 (3)
C2—H20.929C8—H80.948
C3—C41.470 (3)C9—C101.379 (3)
C3—H30.933C9—H90.949
C4—N41.333 (2)C10—H100.932
C4—O41.243 (2)H1—O10.872
C5—C61.396 (3)H4—N40.869
C5—C101.386 (2)H61—N60.879 (15)
C5—N41.425 (2)H62—N60.849 (15)
C6—C71.383 (3)
C2—C1—O1120.3 (2)C6—C7—H7118.5
C2—C1—O2119.8 (2)C8—C7—H7120.5
O1—C1—O2119.9 (2)C7—C8—C9119.90 (19)
C1—C2—C3133.0 (2)C7—C8—H8120
C1—C2—H2112.1C9—C8—H8120.1
C3—C2—H2115C8—C9—C10119.90 (19)
C2—C3—C4128.2 (2)C8—C9—H9119.5
C2—C3—H3117.6C10—C9—H9120.6
C4—C3—H3114.2C5—C10—C9120.29 (17)
C3—C4—N4115.02 (17)C5—C10—H10120.1
C3—C4—O4123.22 (18)C9—C10—H10119.6
N4—C4—O4121.74 (17)C5—N4—C4125.55 (15)
C6—C5—C10120.22 (17)C5—N4—H4116.3
C6—C5—N4117.91 (16)C4—N4—H4118
C10—C5—N4121.85 (16)C6—N6—H61116.5 (14)
C5—C6—C7118.70 (17)C6—N6—H62110.8 (15)
C5—C6—N6120.31 (17)H61—N6—H62116.1 (19)
C7—C6—N6120.95 (18)H1—O1—C1109.5
C6—C7—C8120.98 (19)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O40.871.622.492 (2)174
N4—H4···N6i0.872.173.009 (3)163
N6—H61···O2ii0.878 (19)2.125 (19)2.969 (3)161.0 (19)
C7—H7···O4iii0.952.413.349 (3)166
N6—H62···C9iii0.85 (2)2.77 (2)3.496 (3)144.0 (17)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, y−1/2, −z+3/2.
Selected geometric parameters (Å, °) top
C1—C21.479 (3)C2—C31.339 (3)
C1—O11.301 (3)C3—C41.470 (3)
C1—O21.211 (2)C4—O41.243 (2)
C2—C1—O1120.3 (2)C2—C3—C4128.2 (2)
C2—C1—O2119.8 (2)C3—C4—N4115.02 (17)
O1—C1—O2119.9 (2)C3—C4—O4123.22 (18)
C1—C2—C3133.0 (2)N4—C4—O4121.74 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O40.871.622.492 (2)174
N4—H4···N6i0.872.173.009 (3)163
N6—H61···O2ii0.878 (19)2.125 (19)2.969 (3)161.0 (19)
C7—H7···O4iii0.952.413.349 (3)166
N6—H62···C9iii0.85 (2)2.77 (2)3.496 (3)144.0 (17)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, y−1/2, −z+3/2.
Acknowledgements top

The authors acknowledge Sonia Araceli Sánchez Ruiz, Department of Chemistry, CINVESTAV-IPN, for the acquisition of the MS, IR, 1H and 13C NMR spectra.

references
References top

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