Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046132/zl2058sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046132/zl2058Isup2.hkl |
CCDC reference: 663832
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.
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)].
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.
For related literature, see: Bernstein et al. (1995); Vaupel et al. (2006).
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).
C10H10N2O3 | F(000) = 432 |
Mr = 206.2 | Dx = 1.425 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2535 reflections |
a = 7.3899 (2) Å | θ = 1–29° |
b = 12.2135 (3) Å | µ = 0.11 mm−1 |
c = 12.2633 (3) Å | T = 294 K |
β = 119.726 (1)° | Prism, colourless |
V = 961.19 (4) Å3 | 0.25 × 0.25 × 0.1 mm |
Z = 4 |
Nonius KappaCCD area-detector diffractometer | 1155 reflections with I > 2.5σ(I) |
Radiation source: Enraf–Nonius FR590 | Rint = 0.039 |
Graphite monochromator | θmax = 28.6°, θmin = 2.5° |
Detector resolution: 9 pixels mm-1 | h = −9→9 |
φ and ω scans | k = −16→16 |
4773 measured reflections | l = −16→16 |
2418 independent reflections |
Refinement on F | 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) = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Method = Modified Sheldrick
w = 1/[σ2(F2) + (0.04P)2],
where P = (max(Fo2,0) + 2Fc2)/3 (Sheldrick, 1997) |
1155 reflections | (Δ/σ)max = 0.000165 |
142 parameters | Δρmax = 0.17 e Å−3 |
2 restraints | Δρmin = −0.17 e Å−3 |
C10H10N2O3 | V = 961.19 (4) Å3 |
Mr = 206.2 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.3899 (2) Å | µ = 0.11 mm−1 |
b = 12.2135 (3) Å | T = 294 K |
c = 12.2633 (3) Å | 0.25 × 0.25 × 0.1 mm |
β = 119.726 (1)° |
Nonius KappaCCD area-detector diffractometer | 1155 reflections with I > 2.5σ(I) |
4773 measured reflections | Rint = 0.039 |
2418 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 2 restraints |
wR(F2) = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.17 e Å−3 |
1155 reflections | Δρmin = −0.17 e Å−3 |
142 parameters |
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 | ||
C1 | 0.0694 (3) | 0.9421 (2) | 0.2238 (2) | 0.0631 | |
C2 | 0.1320 (3) | 0.82792 (19) | 0.21902 (19) | 0.0626 | |
C3 | 0.2464 (3) | 0.75461 (18) | 0.30799 (19) | 0.0566 | |
C4 | 0.3461 (3) | 0.76698 (16) | 0.44500 (18) | 0.0479 | |
C5 | 0.5634 (3) | 0.67199 (14) | 0.64461 (16) | 0.0421 | |
C6 | 0.5469 (3) | 0.57449 (15) | 0.69851 (16) | 0.0449 | |
C7 | 0.6578 (3) | 0.56406 (18) | 0.82783 (18) | 0.057 | |
C8 | 0.7808 (3) | 0.64865 (18) | 0.9029 (2) | 0.0633 | |
C9 | 0.7967 (3) | 0.74467 (17) | 0.84874 (19) | 0.0575 | |
C10 | 0.6885 (3) | 0.75622 (15) | 0.71998 (18) | 0.0491 | |
H1 | 0.2094 | 0.9452 | 0.392 | 0.1064* | |
H2 | 0.0782 | 0.8031 | 0.1371 | 0.0719* | |
H3 | 0.2663 | 0.6861 | 0.2818 | 0.0655* | |
H4 | 0.4646 | 0.6245 | 0.4705 | 0.0569* | |
H7 | 0.6456 | 0.4975 | 0.8645 | 0.0697* | |
H8 | 0.8545 | 0.6406 | 0.9915 | 0.0728* | |
H9 | 0.8829 | 0.8021 | 0.9008 | 0.0643* | |
H10 | 0.7023 | 0.8206 | 0.6838 | 0.0573* | |
H61 | 0.316 (3) | 0.5050 (17) | 0.5507 (16) | 0.0671* | |
H62 | 0.409 (3) | 0.4385 (16) | 0.6653 (18) | 0.0687* | |
N4 | 0.4533 (2) | 0.67995 (12) | 0.51109 (13) | 0.0474 | |
N6 | 0.4266 (3) | 0.48726 (14) | 0.62196 (17) | 0.0557 | |
O1 | 0.1358 (2) | 0.99089 (13) | 0.33127 (15) | 0.0797 | |
O2 | −0.0414 (3) | 0.99077 (16) | 0.12712 (16) | 0.0937 | |
O4 | 0.3304 (2) | 0.85106 (12) | 0.49678 (12) | 0.0711 |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0556 (12) | 0.0661 (15) | 0.0542 (14) | −0.0072 (11) | 0.0170 (11) | 0.0160 (12) |
C2 | 0.0636 (12) | 0.0744 (16) | 0.0390 (12) | −0.0143 (12) | 0.0172 (10) | −0.0011 (11) |
C3 | 0.0666 (13) | 0.0534 (13) | 0.0449 (12) | −0.0047 (11) | 0.0240 (11) | −0.0063 (10) |
C4 | 0.0549 (11) | 0.0432 (11) | 0.0430 (11) | −0.0034 (9) | 0.0222 (9) | −0.0036 (9) |
C5 | 0.0471 (10) | 0.0398 (10) | 0.0399 (10) | 0.0036 (8) | 0.0218 (9) | −0.0006 (8) |
C6 | 0.0513 (10) | 0.0395 (10) | 0.0478 (11) | 0.0024 (9) | 0.0276 (9) | −0.0007 (8) |
C7 | 0.0703 (13) | 0.0511 (12) | 0.0524 (12) | 0.0047 (11) | 0.0327 (11) | 0.0069 (10) |
C8 | 0.0742 (14) | 0.0642 (15) | 0.0421 (11) | 0.0112 (12) | 0.0217 (10) | 0.0035 (11) |
C9 | 0.0591 (12) | 0.0517 (13) | 0.0479 (13) | 0.0028 (10) | 0.0160 (10) | −0.0073 (10) |
C10 | 0.0542 (11) | 0.0399 (11) | 0.0499 (12) | −0.0002 (9) | 0.0233 (10) | −0.0017 (9) |
N4 | 0.0635 (10) | 0.0367 (9) | 0.0416 (9) | 0.0011 (8) | 0.0257 (8) | −0.0037 (7) |
N6 | 0.0686 (11) | 0.0415 (10) | 0.0590 (12) | −0.0063 (9) | 0.0331 (10) | −0.0004 (8) |
O1 | 0.0946 (12) | 0.0566 (10) | 0.0640 (11) | 0.0115 (8) | 0.0210 (9) | 0.0103 (8) |
O2 | 0.0916 (12) | 0.0978 (14) | 0.0665 (11) | 0.0065 (10) | 0.0199 (10) | 0.0353 (10) |
O4 | 0.0936 (11) | 0.0542 (9) | 0.0460 (9) | 0.0215 (8) | 0.0197 (8) | −0.0042 (7) |
C1—C2 | 1.479 (3) | C6—N6 | 1.407 (2) |
C1—O1 | 1.301 (3) | C7—C8 | 1.383 (3) |
C1—O2 | 1.211 (2) | C7—H7 | 0.954 |
C2—C3 | 1.339 (3) | C8—C9 | 1.381 (3) |
C2—H2 | 0.929 | C8—H8 | 0.948 |
C3—C4 | 1.470 (3) | C9—C10 | 1.379 (3) |
C3—H3 | 0.933 | C9—H9 | 0.949 |
C4—N4 | 1.333 (2) | C10—H10 | 0.932 |
C4—O4 | 1.243 (2) | H1—O1 | 0.872 |
C5—C6 | 1.396 (3) | H4—N4 | 0.869 |
C5—C10 | 1.386 (2) | H61—N6 | 0.879 (15) |
C5—N4 | 1.425 (2) | H62—N6 | 0.849 (15) |
C6—C7 | 1.383 (3) | ||
C2—C1—O1 | 120.3 (2) | C6—C7—H7 | 118.5 |
C2—C1—O2 | 119.8 (2) | C8—C7—H7 | 120.5 |
O1—C1—O2 | 119.9 (2) | C7—C8—C9 | 119.90 (19) |
C1—C2—C3 | 133.0 (2) | C7—C8—H8 | 120 |
C1—C2—H2 | 112.1 | C9—C8—H8 | 120.1 |
C3—C2—H2 | 115 | C8—C9—C10 | 119.90 (19) |
C2—C3—C4 | 128.2 (2) | C8—C9—H9 | 119.5 |
C2—C3—H3 | 117.6 | C10—C9—H9 | 120.6 |
C4—C3—H3 | 114.2 | C5—C10—C9 | 120.29 (17) |
C3—C4—N4 | 115.02 (17) | C5—C10—H10 | 120.1 |
C3—C4—O4 | 123.22 (18) | C9—C10—H10 | 119.6 |
N4—C4—O4 | 121.74 (17) | C5—N4—C4 | 125.55 (15) |
C6—C5—C10 | 120.22 (17) | C5—N4—H4 | 116.3 |
C6—C5—N4 | 117.91 (16) | C4—N4—H4 | 118 |
C10—C5—N4 | 121.85 (16) | C6—N6—H61 | 116.5 (14) |
C5—C6—C7 | 118.70 (17) | C6—N6—H62 | 110.8 (15) |
C5—C6—N6 | 120.31 (17) | H61—N6—H62 | 116.1 (19) |
C7—C6—N6 | 120.95 (18) | H1—O1—C1 | 109.5 |
C6—C7—C8 | 120.98 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4 | 0.87 | 1.62 | 2.492 (2) | 174 |
N4—H4···N6i | 0.87 | 2.17 | 3.009 (3) | 163 |
N6—H61···O2ii | 0.878 (19) | 2.125 (19) | 2.969 (3) | 161.0 (19) |
C7—H7···O4iii | 0.95 | 2.41 | 3.349 (3) | 166 |
N6—H62···C9iii | 0.85 (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. |
Experimental details
Crystal data | |
Chemical formula | C10H10N2O3 |
Mr | 206.2 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 294 |
a, b, c (Å) | 7.3899 (2), 12.2135 (3), 12.2633 (3) |
β (°) | 119.726 (1) |
V (Å3) | 961.19 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.25 × 0.25 × 0.1 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2.5σ(I)] reflections | 4773, 2418, 1155 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.674 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.051, 1.01 |
No. of reflections | 1155 |
No. of parameters | 142 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.17 |
Computer programs: COLLECT (Nonius, 2001), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996), PLATON (Spek, 2003).
C1—C2 | 1.479 (3) | C2—C3 | 1.339 (3) |
C1—O1 | 1.301 (3) | C3—C4 | 1.470 (3) |
C1—O2 | 1.211 (2) | C4—O4 | 1.243 (2) |
C2—C1—O1 | 120.3 (2) | C2—C3—C4 | 128.2 (2) |
C2—C1—O2 | 119.8 (2) | C3—C4—N4 | 115.02 (17) |
O1—C1—O2 | 119.9 (2) | C3—C4—O4 | 123.22 (18) |
C1—C2—C3 | 133.0 (2) | N4—C4—O4 | 121.74 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4 | 0.87 | 1.62 | 2.492 (2) | 174 |
N4—H4···N6i | 0.87 | 2.17 | 3.009 (3) | 163 |
N6—H61···O2ii | 0.878 (19) | 2.125 (19) | 2.969 (3) | 161.0 (19) |
C7—H7···O4iii | 0.95 | 2.41 | 3.349 (3) | 166 |
N6—H62···C9iii | 0.85 (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. |
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.