Acta Cryst. (2009). E65, o1244 [ doi:10.1107/S1600536809016870 ]
In the crystal structure of the title compound, C9H10N2O3, the molecules are linked by intermolecular O-H
N and N-HO hydrogen bonds, resulting in chains propagating in [010]. Weak intramolecular and intermolecular C-HO interactions are also observed.
A solution of pyrrolidine-2,5-dione (1.0 g,10 mmol) in dimethylformamide (15 ml) was stirred at room temperature for 10 min. Pyridin-2-amine (0.94 g, 10 mmol) was added and the mixture was stirred for a further 3 h at 353 K. The resulting mixture was then poured into water (100 ml), yielding a white precipitate. The solid product was filtered off, washed with cold water and recrystallized from methnol, giving crystals of the title compound [yield: 1.17 g (61.4%)]. These were dissolved in mixture of methnol (10 ml) and water (3 ml) and the solution was kept at room temperature for 18 d. Natural evaporation of the solution gave colourless prisms of (I) (m.p. 454–455 K).
The O- and N-bound H atoms were located in a difference map and their positions and Uiso values were freely refined. The C-bound H atoms were geometrically placed (C—H = 0.95–0.99Å) and refined as riding with Uiso(H) = 1.2Ueq(C).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CrystalStructure (Rigaku, 2005).
![[Figure 1]](./hb2960fig1thm.gif)
| Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level (arbitrary spheres for H atoms). |
![[Figure 2]](./hb2960fig2thm.gif)
| Fig. 2. Part of the crystal structure of (I), with hydrogen bonds shown as dashed lines. |
| C9H10N2O3 | F000 = 408 |
| Mr = 194.19 | Dx = 1.450 Mg m−3 |
| Monoclinic, P21/n | Melting point = 454–455 K |
| Hall symbol: -P 2yn | Mo Kα radiation λ = 0.71070 Å |
| a = 12.7384 (10) Å | Cell parameters from 2970 reflections |
| b = 5.0485 (5) Å | θ = 2.1–27.2º |
| c = 13.8463 (12) Å | µ = 0.11 mm−1 |
| β = 92.924 (8)º | T = 113 K |
| V = 889.29 (14) Å3 | Prism, colourless |
| Z = 4 | 0.22 × 0.04 × 0.03 mm |
| Rigaku Saturn diffractometer | 1972 independent reflections |
| Radiation source: rotating anode | 1297 reflections with I > 2σ(I) |
| Monochromator: confocal | Rint = 0.074 |
| Detector resolution: 14.63 pixels mm-1 | θmax = 27.2º |
| T = 113 K | θmin = 2.1º |
| ω and φ scans | h = −16→16 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −6→6 |
| Tmin = 0.995, Tmax = 0.996 | l = −17→17 |
| 8079 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0361P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.97 | (Δ/σ)max = 0.001 |
| 1972 reflections | Δρmax = 0.23 e Å−3 |
| 135 parameters | Δρmin = −0.22 e Å−3 |
| 1 restraint | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.041 (3) |
| C9H10N2O3 | V = 889.29 (14) Å3 |
| Mr = 194.19 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 12.7384 (10) Å | µ = 0.11 mm−1 |
| b = 5.0485 (5) Å | T = 113 K |
| c = 13.8463 (12) Å | 0.22 × 0.04 × 0.03 mm |
| β = 92.924 (8)º |
| Rigaku Saturn diffractometer | 1972 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1297 reflections with I > 2σ(I) |
| Tmin = 0.995, Tmax = 0.996 | Rint = 0.074 |
| 8079 measured reflections |
| R[F2 > 2σ(F2)] = 0.048 | 1 restraint |
| wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.97 | Δρmax = 0.23 e Å−3 |
| 1972 reflections | Δρmin = −0.22 e Å−3 |
| 135 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 | ||
| O1 | 0.44178 (10) | 0.2594 (3) | 0.58044 (9) | 0.0272 (4) | |
| H1 | 0.4642 (15) | 0.145 (4) | 0.6323 (13) | 0.041* | |
| O2 | 0.34511 (10) | 0.4177 (3) | 0.69759 (9) | 0.0290 (4) | |
| O3 | 0.12611 (10) | 0.3483 (3) | 0.52083 (9) | 0.0284 (4) | |
| N1 | 0.08391 (12) | 0.5393 (3) | 0.66376 (11) | 0.0216 (4) | |
| N2 | −0.02347 (12) | 0.4254 (3) | 0.78432 (11) | 0.0231 (4) | |
| C1 | 0.37059 (14) | 0.4218 (4) | 0.61433 (13) | 0.0221 (4) | |
| C2 | 0.32399 (15) | 0.6117 (4) | 0.54040 (13) | 0.0239 (5) | |
| H2A | 0.3090 | 0.5171 | 0.4786 | 0.029* | |
| H2B | 0.3753 | 0.7541 | 0.5288 | 0.029* | |
| C3 | 0.22283 (14) | 0.7334 (4) | 0.57436 (13) | 0.0227 (5) | |
| H3A | 0.2367 | 0.8194 | 0.6380 | 0.027* | |
| H3B | 0.1972 | 0.8703 | 0.5277 | 0.027* | |
| C4 | 0.14010 (14) | 0.5211 (4) | 0.58271 (13) | 0.0223 (5) | |
| C5 | 0.00578 (14) | 0.3716 (4) | 0.69450 (13) | 0.0214 (5) | |
| C6 | −0.04012 (15) | 0.1661 (4) | 0.63919 (13) | 0.0244 (5) | |
| H6 | −0.0190 | 0.1317 | 0.5756 | 0.029* | |
| C7 | −0.11649 (15) | 0.0153 (4) | 0.67911 (14) | 0.0265 (5) | |
| H7 | −0.1484 | −0.1261 | 0.6431 | 0.032* | |
| C8 | −0.14707 (15) | 0.0686 (4) | 0.77148 (13) | 0.0276 (5) | |
| H8 | −0.1999 | −0.0338 | 0.7999 | 0.033* | |
| C9 | −0.09839 (15) | 0.2750 (4) | 0.82096 (13) | 0.0256 (5) | |
| H9 | −0.1190 | 0.3126 | 0.8845 | 0.031* | |
| H1A | 0.1087 (16) | 0.673 (4) | 0.7090 (14) | 0.043 (6)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0313 (8) | 0.0289 (8) | 0.0218 (8) | 0.0121 (7) | 0.0044 (6) | 0.0043 (6) |
| O2 | 0.0352 (8) | 0.0350 (9) | 0.0172 (7) | 0.0102 (7) | 0.0057 (6) | 0.0054 (6) |
| O3 | 0.0363 (9) | 0.0269 (8) | 0.0221 (8) | 0.0033 (6) | 0.0026 (6) | −0.0067 (6) |
| N1 | 0.0237 (9) | 0.0228 (10) | 0.0185 (8) | −0.0006 (7) | 0.0019 (7) | −0.0045 (7) |
| N2 | 0.0259 (9) | 0.0232 (9) | 0.0202 (8) | −0.0010 (8) | 0.0006 (7) | −0.0007 (7) |
| C1 | 0.0223 (10) | 0.0217 (11) | 0.0222 (10) | −0.0005 (9) | 0.0007 (8) | −0.0010 (9) |
| C2 | 0.0282 (11) | 0.0246 (11) | 0.0191 (10) | 0.0051 (9) | 0.0028 (8) | 0.0020 (8) |
| C3 | 0.0274 (11) | 0.0213 (11) | 0.0191 (10) | 0.0043 (9) | 0.0000 (8) | 0.0009 (8) |
| C4 | 0.0257 (11) | 0.0208 (11) | 0.0200 (10) | 0.0074 (9) | −0.0031 (8) | 0.0008 (8) |
| C5 | 0.0234 (11) | 0.0214 (11) | 0.0191 (10) | 0.0037 (9) | −0.0021 (8) | 0.0005 (8) |
| C6 | 0.0283 (12) | 0.0237 (11) | 0.0207 (10) | 0.0042 (9) | −0.0033 (8) | −0.0034 (8) |
| C7 | 0.0299 (11) | 0.0235 (12) | 0.0252 (11) | 0.0008 (9) | −0.0063 (9) | −0.0041 (9) |
| C8 | 0.0320 (12) | 0.0238 (11) | 0.0267 (11) | −0.0057 (9) | −0.0023 (9) | 0.0030 (9) |
| C9 | 0.0311 (12) | 0.0253 (12) | 0.0203 (10) | −0.0022 (9) | 0.0008 (8) | −0.0008 (9) |
| O1—C1 | 1.326 (2) | C2—H2B | 0.9900 |
| O1—H1 | 0.954 (17) | C3—C4 | 1.512 (3) |
| O2—C1 | 1.214 (2) | C3—H3A | 0.9900 |
| O3—C4 | 1.229 (2) | C3—H3B | 0.9900 |
| N1—C4 | 1.365 (2) | C5—C6 | 1.400 (2) |
| N1—C5 | 1.390 (2) | C6—C7 | 1.373 (3) |
| N1—H1A | 0.96 (2) | C6—H6 | 0.9500 |
| N2—C9 | 1.340 (2) | C7—C8 | 1.382 (2) |
| N2—C5 | 1.344 (2) | C7—H7 | 0.9500 |
| C1—C2 | 1.503 (2) | C8—C9 | 1.377 (2) |
| C2—C3 | 1.523 (2) | C8—H8 | 0.9500 |
| C2—H2A | 0.9900 | C9—H9 | 0.9500 |
| C1—O1—H1 | 107.1 (12) | H3A—C3—H3B | 108.2 |
| C4—N1—C5 | 128.65 (17) | O3—C4—N1 | 123.90 (19) |
| C4—N1—H1A | 114.5 (12) | O3—C4—C3 | 121.78 (18) |
| C5—N1—H1A | 116.3 (12) | N1—C4—C3 | 114.33 (16) |
| C9—N2—C5 | 118.17 (16) | N2—C5—N1 | 113.37 (16) |
| O2—C1—O1 | 123.11 (17) | N2—C5—C6 | 121.90 (18) |
| O2—C1—C2 | 122.87 (17) | N1—C5—C6 | 124.73 (17) |
| O1—C1—C2 | 114.02 (16) | C7—C6—C5 | 118.38 (18) |
| C1—C2—C3 | 110.98 (16) | C7—C6—H6 | 120.8 |
| C1—C2—H2A | 109.4 | C5—C6—H6 | 120.8 |
| C3—C2—H2A | 109.4 | C6—C7—C8 | 120.21 (18) |
| C1—C2—H2B | 109.4 | C6—C7—H7 | 119.9 |
| C3—C2—H2B | 109.4 | C8—C7—H7 | 119.9 |
| H2A—C2—H2B | 108.0 | C9—C8—C7 | 117.82 (18) |
| C4—C3—C2 | 109.99 (15) | C9—C8—H8 | 121.1 |
| C4—C3—H3A | 109.7 | C7—C8—H8 | 121.1 |
| C2—C3—H3A | 109.7 | N2—C9—C8 | 123.51 (18) |
| C4—C3—H3B | 109.7 | N2—C9—H9 | 118.2 |
| C2—C3—H3B | 109.7 | C8—C9—H9 | 118.2 |
| O2—C1—C2—C3 | −16.5 (3) | C4—N1—C5—N2 | 171.25 (17) |
| O1—C1—C2—C3 | 163.40 (16) | C4—N1—C5—C6 | −9.1 (3) |
| C1—C2—C3—C4 | −64.77 (19) | N2—C5—C6—C7 | −0.6 (3) |
| C5—N1—C4—O3 | 2.5 (3) | N1—C5—C6—C7 | 179.81 (16) |
| C5—N1—C4—C3 | −177.43 (15) | C5—C6—C7—C8 | 0.5 (3) |
| C2—C3—C4—O3 | −42.8 (2) | C6—C7—C8—C9 | −0.2 (3) |
| C2—C3—C4—N1 | 137.14 (15) | C5—N2—C9—C8 | −0.1 (3) |
| C9—N2—C5—N1 | −179.95 (15) | C7—C8—C9—N2 | 0.0 (3) |
| C9—N2—C5—C6 | 0.4 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N2i | 0.954 (19) | 1.744 (19) | 2.690 (2) | 170.4 (17) |
| N1—H1A···O2ii | 0.96 (2) | 1.86 (2) | 2.824 (2) | 176.6 (19) |
| C6—H6···O3 | 0.95 | 2.31 | 2.893 (2) | 119 |
| C3—H3A···O2ii | 0.99 | 2.60 | 3.445 (2) | 143 |
| C3—H3B···O3iii | 0.99 | 2.58 | 3.408 (2) | 141 |
| C7—H7···O3iv | 0.95 | 2.56 | 3.319 (2) | 137 |
| Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x, y+1, z; (iv) −x, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N2i | 0.954 (19) | 1.744 (19) | 2.690 (2) | 170.4 (17) |
| N1—H1A···O2ii | 0.96 (2) | 1.86 (2) | 2.824 (2) | 176.6 (19) |
| C6—H6···O3 | 0.95 | 2.31 | 2.893 (2) | 119 |
| C3—H3A···O2ii | 0.99 | 2.60 | 3.445 (2) | 143 |
| C3—H3B···O3iii | 0.99 | 2.58 | 3.408 (2) | 141 |
| C7—H7···O3iv | 0.95 | 2.56 | 3.319 (2) | 137 |
| Symmetry codes: (i) −x+1/2, y−1/2, −z+3/2; (ii) −x+1/2, y+1/2, −z+3/2; (iii) x, y+1, z; (iv) −x, −y, −z+1. |
Narendar, P., Parthiban, J. & Anbalagan, N. (2003). Biol. Pharm. Bull. 26, 182–187.
Ravlee, I., Sivakumar, R. & Muruganantham, N. (2003). Chem. Pharm. Bull. 51, 162–170.
Rigaku (2005). CrystalClear and CrystalStructure. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Pyridine derivatives substituted by N-alkylation show useful pharmaceutical properties (Narendar et al., 2003; Ravlee et al., 2003). In this paper, the structure of 4-oxo-4-(pyridin-2-ylamino)butanoic acid (I), is reported which was synthesized by acylating reation of pyridin-2-amine with pyrrolidine-2,5-dione. The pyridin ring system is essentially planar with mean deviations of 0.0013 Å. In addition, there are C—H···O interactions, as shown in Fig. 2 and detailed in Table 1.