Acta Cryst. (2008). E64, o2264 [ doi:10.1107/S1600536808035538 ]
The title compound, C7H9N3O2, was prepared by alkaline hydrolysis of ethyl 1-allyl-3-amino-1H-pyrazole-4-carboxylate. The crystal structure is stabilized by three types of intermolecular hydrogen bond (N-H
O, N-HN and O-HN).
The mixture of ethyl 1-allyl-3-amino-1H-pyrazole-4-carboxylate (1.95 g, 10 mmol) in THF-MeOH (50 ml, v/v = 1/1) with 2.5N NaOH(25 ml) was heated at 333 K for 4 h. The solvent was removed under reduced pressure and the residue was acidified with 6N HCl at 273 K. A gray solid was precipitated, filtered, and washed with water. Single crystals suitable for X-ray diffraction were obtained by recrystallization of the title compound in ethanol.
H atoms of N1 and O2 were positioned in a difference Fourier maps and their parameters were freely refined. The other H atoms were placed in calculated positions, with C—H = 0.95 or 0.99 Å, and and O—H = 0.82 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq(C).
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).
![[Figure 1]](./lx2076fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. |
![[Figure 2]](./lx2076fig2thm.gif)
| Fig. 2. Hydrogenbonds interactions (dotted lines) in the title compound. [symmetry code; (i) -x+1, y-1/2, -z+3/2; (ii) -x+1, y+1/2, -z+3/2; (iii) x, -y+3/2, z-1/2.] |
| C7H9N3O2 | F(000) = 352 |
| Mr = 167.17 | Dx = 1.421 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2299 reflections |
| a = 8.966 (2) Å | θ = 2.4–27.9° |
| b = 8.531 (2) Å | µ = 0.11 mm−1 |
| c = 10.266 (2) Å | T = 113 K |
| β = 95.57 (3)° | Prism, colorless |
| V = 781.5 (3) Å3 | 0.20 × 0.18 × 0.14 mm |
| Z = 4 |
| Rigaku Saturn CCD area-detector diffractometer | 1852 independent reflections |
| Radiation source: rotating anode | 1631 reflections with I > 2σ(I) |
| confocal | Rint = 0.025 |
| Detector resolution: 7.31 pixels mm-1 | θmax = 27.9°, θmin = 3.1° |
| ω and φ scans | h = −7→11 |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −11→11 |
| Tmin = 0.979, Tmax = 0.985 | l = −13→13 |
| 5773 measured reflections |
| 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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0353P)2 + 0.3376P] where P = (Fo2 + 2Fc2)/3 |
| 1852 reflections | (Δ/σ)max < 0.001 |
| 121 parameters | Δρmax = 0.28 e Å−3 |
| 0 restraints | Δρmin = −0.25 e Å−3 |
| C7H9N3O2 | V = 781.5 (3) Å3 |
| Mr = 167.17 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.966 (2) Å | µ = 0.11 mm−1 |
| b = 8.531 (2) Å | T = 113 K |
| c = 10.266 (2) Å | 0.20 × 0.18 × 0.14 mm |
| β = 95.57 (3)° |
| Rigaku Saturn CCD area-detector diffractometer | 1852 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1631 reflections with I > 2σ(I) |
| Tmin = 0.979, Tmax = 0.985 | Rint = 0.025 |
| 5773 measured reflections | θmax = 27.9° |
| R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.085 | Δρmax = 0.28 e Å−3 |
| S = 1.06 | Δρmin = −0.25 e Å−3 |
| 1852 reflections | Absolute structure: ? |
| 121 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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. |
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.64833 (12) | 0.69316 (12) | 0.51583 (10) | 0.0123 (2) | |
| C2 | 0.68026 (12) | 0.53444 (13) | 0.56126 (10) | 0.0122 (2) | |
| C3 | 0.63332 (12) | 0.46275 (12) | 0.67507 (10) | 0.0116 (2) | |
| C4 | 0.75001 (12) | 0.41422 (13) | 0.49875 (10) | 0.0134 (2) | |
| H4 | 0.7935 | 0.4217 | 0.4182 | 0.016* | |
| C5 | 0.79757 (13) | 0.12954 (13) | 0.54567 (11) | 0.0149 (2) | |
| H5A | 0.8212 | 0.1241 | 0.4536 | 0.018* | |
| H5B | 0.7169 | 0.0529 | 0.5570 | 0.018* | |
| C6 | 0.93408 (13) | 0.08629 (14) | 0.63419 (11) | 0.0177 (2) | |
| H6 | 1.0204 | 0.1508 | 0.6340 | 0.021* | |
| C7 | 0.94070 (15) | −0.03654 (16) | 0.71224 (12) | 0.0238 (3) | |
| H7A | 0.8560 | −0.1030 | 0.7143 | 0.029* | |
| H7B | 1.0302 | −0.0587 | 0.7665 | 0.029* | |
| N1 | 0.55906 (11) | 0.53395 (11) | 0.77249 (9) | 0.0132 (2) | |
| H1A | 0.5169 (17) | 0.4628 (18) | 0.8213 (15) | 0.024 (4)* | |
| H1B | 0.4929 (18) | 0.6087 (19) | 0.7423 (15) | 0.025 (4)* | |
| N2 | 0.67310 (10) | 0.31234 (11) | 0.68348 (9) | 0.0128 (2) | |
| N3 | 0.74458 (10) | 0.28673 (11) | 0.57279 (9) | 0.0128 (2) | |
| O1 | 0.57152 (9) | 0.78485 (9) | 0.57215 (8) | 0.01648 (19) | |
| O2 | 0.70880 (9) | 0.72908 (10) | 0.40620 (8) | 0.01749 (19) | |
| H2A | 0.663 (2) | 0.818 (2) | 0.3719 (19) | 0.049 (5)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0129 (5) | 0.0125 (5) | 0.0113 (5) | −0.0016 (4) | 0.0006 (4) | 0.0004 (4) |
| C2 | 0.0130 (5) | 0.0122 (5) | 0.0114 (5) | 0.0000 (4) | 0.0007 (4) | 0.0000 (4) |
| C3 | 0.0118 (5) | 0.0113 (5) | 0.0114 (5) | −0.0008 (4) | 0.0001 (4) | −0.0012 (4) |
| C4 | 0.0141 (5) | 0.0142 (5) | 0.0119 (5) | 0.0006 (4) | 0.0016 (4) | 0.0012 (4) |
| C5 | 0.0187 (5) | 0.0114 (5) | 0.0151 (5) | 0.0026 (4) | 0.0029 (4) | −0.0025 (4) |
| C6 | 0.0151 (5) | 0.0168 (6) | 0.0215 (5) | 0.0026 (4) | 0.0032 (4) | −0.0032 (4) |
| C7 | 0.0237 (6) | 0.0262 (7) | 0.0216 (6) | 0.0075 (5) | 0.0021 (5) | 0.0031 (5) |
| N1 | 0.0170 (5) | 0.0104 (4) | 0.0127 (4) | 0.0009 (4) | 0.0043 (4) | 0.0006 (3) |
| N2 | 0.0148 (4) | 0.0124 (5) | 0.0114 (4) | 0.0007 (3) | 0.0032 (3) | −0.0012 (3) |
| N3 | 0.0146 (4) | 0.0124 (5) | 0.0116 (4) | 0.0015 (3) | 0.0027 (3) | −0.0010 (3) |
| O1 | 0.0215 (4) | 0.0125 (4) | 0.0160 (4) | 0.0026 (3) | 0.0048 (3) | −0.0005 (3) |
| O2 | 0.0216 (4) | 0.0160 (4) | 0.0160 (4) | 0.0043 (3) | 0.0077 (3) | 0.0058 (3) |
| C1—O1 | 1.2238 (13) | C5—H5A | 0.9900 |
| C1—O2 | 1.3316 (13) | C5—H5B | 0.9900 |
| C1—C2 | 1.4516 (15) | C6—C7 | 1.3170 (17) |
| C2—C4 | 1.3902 (15) | C6—H6 | 0.9500 |
| C2—C3 | 1.4182 (14) | C7—H7A | 0.9500 |
| C3—N2 | 1.3323 (14) | C7—H7B | 0.9500 |
| C3—N1 | 1.3936 (14) | N1—H1A | 0.894 (16) |
| C4—N3 | 1.3305 (14) | N1—H1B | 0.905 (17) |
| C4—H4 | 0.9500 | N2—N3 | 1.3752 (13) |
| C5—N3 | 1.4585 (14) | O2—H2A | 0.92 (2) |
| C5—C6 | 1.4980 (16) | ||
| O1—C1—O2 | 123.11 (10) | C6—C5—H5B | 109.2 |
| O1—C1—C2 | 123.16 (10) | H5A—C5—H5B | 107.9 |
| O2—C1—C2 | 113.73 (9) | C7—C6—C5 | 123.43 (11) |
| C4—C2—C3 | 104.18 (9) | C7—C6—H6 | 118.3 |
| C4—C2—C1 | 128.56 (10) | C5—C6—H6 | 118.3 |
| C3—C2—C1 | 127.00 (10) | C6—C7—H7A | 120.0 |
| N2—C3—N1 | 121.12 (10) | C6—C7—H7B | 120.0 |
| N2—C3—C2 | 111.70 (9) | H7A—C7—H7B | 120.0 |
| N1—C3—C2 | 127.15 (10) | C3—N1—H1A | 111.3 (10) |
| N3—C4—C2 | 107.24 (9) | C3—N1—H1B | 113.8 (10) |
| N3—C4—H4 | 126.4 | H1A—N1—H1B | 111.8 (14) |
| C2—C4—H4 | 126.4 | C3—N2—N3 | 104.05 (9) |
| N3—C5—C6 | 111.89 (9) | C4—N3—N2 | 112.83 (9) |
| N3—C5—H5A | 109.2 | C4—N3—C5 | 127.73 (9) |
| C6—C5—H5A | 109.2 | N2—N3—C5 | 119.37 (9) |
| N3—C5—H5B | 109.2 | C1—O2—H2A | 108.1 (12) |
| O1—C1—C2—C4 | 171.64 (11) | N3—C5—C6—C7 | 121.64 (12) |
| O2—C1—C2—C4 | −7.54 (16) | N1—C3—N2—N3 | −178.90 (9) |
| O1—C1—C2—C3 | −1.60 (17) | C2—C3—N2—N3 | −0.81 (12) |
| O2—C1—C2—C3 | 179.22 (10) | C2—C4—N3—N2 | 0.52 (12) |
| C4—C2—C3—N2 | 1.12 (12) | C2—C4—N3—C5 | 177.29 (10) |
| C1—C2—C3—N2 | 175.67 (10) | C3—N2—N3—C4 | 0.18 (12) |
| C4—C2—C3—N1 | 179.07 (10) | C3—N2—N3—C5 | −176.89 (9) |
| C1—C2—C3—N1 | −6.38 (18) | C6—C5—N3—C4 | 109.64 (12) |
| C3—C2—C4—N3 | −0.95 (12) | C6—C5—N3—N2 | −73.77 (12) |
| C1—C2—C4—N3 | −175.38 (10) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1i | 0.894 (16) | 2.073 (16) | 2.9652 (13) | 175.7 (14) |
| N1—H1B···N2ii | 0.905 (17) | 2.457 (16) | 3.2187 (14) | 142.1 (13) |
| O2—H2A···N1iii | 0.92 (2) | 1.82 (2) | 2.7232 (14) | 166.8 (18) |
| Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y+3/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1i | 0.894 (16) | 2.073 (16) | 2.9652 (13) | 175.7 (14) |
| N1—H1B···N2ii | 0.905 (17) | 2.457 (16) | 3.2187 (14) | 142.1 (13) |
| O2—H2A···N1iii | 0.92 (2) | 1.82 (2) | 2.7232 (14) | 166.8 (18) |
| Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) x, −y+3/2, z−1/2. |
This work was supported by the Program for New Century Excellent Talents in Universities of Henan Province (grant No. 2005HANCET-17), the Natural Science Foundation of Henan Province (grant No. 082300420110) and the Natural Science Foundation of Henan Province Eduation Department (grant No. 2007150036).
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Pyrazole ring derivatives are very important substances in biology and have many application in the field of pesticide and pharmaceutical agents (Malhotra et al., 1997; Takao et al., 1994). Some of these compounds such as pyrazosufuron have been sold as agrochemicals (Wang et al., 2005).
Here we report the synthesis and crystal structure of the title compound, 1-allyl-3-amino-1H-pyrazole-4-carboxylic acid (Fig. 1). The crystal packing (Fig. 2) is stabilized by the intermolecular hydrogen bonds (Fig. 2 & Table 1).