Acta Cryst. (2009). E65, o2442 [ doi:10.1107/S160053680903342X ]
In the crystal of the title compound, C8H13N3O, molecules are linked by intermolecular N-H
N and N-HO hydrogen bonds into a three-dimensional network. Additional stabilization is provided by weak intermolecular C-HO hydrogen bonds.
A mixture of 3,5-dimethylpyrazole (3.845 g, 40 mmol), sodium hydroxide (0.2 g, 5 mmol) and N,N'-dimethylformamide(DMF)(100 ml) was stirred and heated to 373 K. A solution of acrylamide (2.843 g, 40 mmol) in DMF (20 ml) was added dropwise. After 6 h, heating was then terminated. The cooled reaction mixture was filtered and DMF was removed by vacuum distillation to give 3.66 g analytically pure N-pyrazolylpropanimide (yield: 54.7%). Recrystallization from ethanol solution yielded colorless single-crystals suitable for X-ray diffraction analysis. Calculated for C8H13N3O: C 57.42, H 7.78, N 25.12%; found: C 57.26, H 7.59, N 25.18%.
H atoms were positioned geometrically and treated in the subsequent refinement as riding atoms, with C—H = 0.93 (aromatic), 0.97 Å (methylene), 0.96 (methyl) and N—H = 0.86 Å, and with Uiso(H) = 1.2 Ueq(C,N) or 1.5 Ueq(Cmethyl). In the absense of significant anomalous dispersion effects Friedel pairs were merged.
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); 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: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./lh2847fig1thm.gif)
| Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./lh2847fig2thm.gif)
| Fig. 2. Part of the crystal structure of the title compound. Dashed lines indicate hydrogen bonds. |
| C8H13N3O | F(000) = 1440 |
| Mr = 167.21 | Dx = 1.238 Mg m−3 |
| Orthorhombic, Fdd2 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: F 2 -2d | Cell parameters from 4623 reflections |
| a = 14.452 (5) Å | θ = 3.1–27.5° |
| b = 33.390 (7) Å | µ = 0.09 mm−1 |
| c = 7.4354 (15) Å | T = 298 K |
| V = 3588.0 (16) Å3 | Block, colorless |
| Z = 16 | 0.47 × 0.37 × 0.36 mm |
| Rigaku R-AXIS RAPID diffractometer | 1067 independent reflections |
| Radiation source: fine-focus sealed tube | 890 reflections with I > 2σ(I) |
| graphite | Rint = 0.044 |
| Detector resolution: 0 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
| ω scans | h = −17→18 |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −43→43 |
| Tmin = 0.963, Tmax = 0.970 | l = −9→8 |
| 4623 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)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0446P)2 + 1.8694P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.14 | (Δ/σ)max < 0.001 |
| 1067 reflections | Δρmax = 0.14 e Å−3 |
| 112 parameters | Δρmin = −0.19 e Å−3 |
| 1 restraint | Extinction correction: SHELXTL'(Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0108 (8) |
| C8H13N3O | V = 3588.0 (16) Å3 |
| Mr = 167.21 | Z = 16 |
| Orthorhombic, Fdd2 | Mo Kα radiation |
| a = 14.452 (5) Å | µ = 0.09 mm−1 |
| b = 33.390 (7) Å | T = 298 K |
| c = 7.4354 (15) Å | 0.47 × 0.37 × 0.36 mm |
| Rigaku R-AXIS RAPID diffractometer | 1067 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 890 reflections with I > 2σ(I) |
| Tmin = 0.963, Tmax = 0.970 | Rint = 0.044 |
| 4623 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
| wR(F2) = 0.093 | Δρmax = 0.14 e Å−3 |
| S = 1.14 | Δρmin = −0.19 e Å−3 |
| 1067 reflections | Absolute structure: ? |
| 112 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
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 | 0.02008 (12) | 0.12376 (4) | 0.3335 (3) | 0.0530 (5) | |
| N1 | −0.08464 (14) | 0.07777 (6) | 0.2532 (4) | 0.0530 (6) | |
| H1A | −0.1185 | 0.0952 | 0.1991 | 0.064* | |
| H1B | −0.1013 | 0.0530 | 0.2556 | 0.064* | |
| N2 | 0.15555 (13) | 0.04420 (5) | 0.1786 (2) | 0.0364 (5) | |
| N3 | 0.12698 (13) | 0.00771 (5) | 0.1195 (3) | 0.0413 (5) | |
| C1 | −0.00707 (15) | 0.08880 (6) | 0.3326 (3) | 0.0380 (5) | |
| C2 | 0.04624 (16) | 0.05620 (6) | 0.4265 (3) | 0.0435 (6) | |
| H2A | 0.0163 | 0.0307 | 0.4032 | 0.052* | |
| H2B | 0.0441 | 0.0609 | 0.5551 | 0.052* | |
| C3 | 0.14666 (15) | 0.05349 (7) | 0.3680 (3) | 0.0391 (5) | |
| H3B | 0.1771 | 0.0788 | 0.3924 | 0.047* | |
| H3A | 0.1775 | 0.0329 | 0.4379 | 0.047* | |
| C4 | 0.2226 (2) | 0.10885 (7) | 0.0702 (5) | 0.0622 (8) | |
| H4B | 0.2746 | 0.1082 | 0.1504 | 0.093* | |
| H4C | 0.1747 | 0.1253 | 0.1210 | 0.093* | |
| H4A | 0.2414 | 0.1198 | −0.0434 | 0.093* | |
| C5 | 0.18687 (15) | 0.06742 (6) | 0.0435 (3) | 0.0422 (5) | |
| C6 | 0.17798 (19) | 0.04516 (8) | −0.1109 (4) | 0.0505 (6) | |
| H6A | 0.1938 | 0.0529 | −0.2270 | 0.061* | |
| C7 | 0.14038 (16) | 0.00856 (7) | −0.0582 (3) | 0.0438 (6) | |
| C8 | 0.1147 (2) | −0.02660 (9) | −0.1705 (5) | 0.0628 (8) | |
| H8A | 0.1465 | −0.0499 | −0.1274 | 0.094* | |
| H8B | 0.1319 | −0.0217 | −0.2932 | 0.094* | |
| H8C | 0.0491 | −0.0309 | −0.1634 | 0.094* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0548 (10) | 0.0323 (7) | 0.0719 (13) | −0.0018 (6) | −0.0196 (10) | −0.0002 (8) |
| N1 | 0.0488 (10) | 0.0381 (9) | 0.0720 (16) | −0.0038 (8) | −0.0163 (12) | 0.0039 (11) |
| N2 | 0.0386 (10) | 0.0338 (10) | 0.0369 (10) | 0.0008 (7) | −0.0009 (9) | −0.0020 (8) |
| N3 | 0.0410 (10) | 0.0342 (9) | 0.0486 (12) | 0.0007 (7) | −0.0011 (10) | −0.0057 (8) |
| C1 | 0.0391 (11) | 0.0335 (9) | 0.0415 (12) | 0.0025 (8) | 0.0025 (10) | −0.0037 (9) |
| C2 | 0.0473 (13) | 0.0385 (11) | 0.0447 (13) | 0.0024 (9) | 0.0045 (11) | 0.0049 (10) |
| C3 | 0.0419 (12) | 0.0367 (10) | 0.0387 (12) | 0.0061 (9) | −0.0027 (11) | −0.0005 (9) |
| C4 | 0.0787 (19) | 0.0442 (13) | 0.0636 (18) | −0.0134 (12) | 0.0057 (17) | 0.0057 (13) |
| C5 | 0.0425 (11) | 0.0419 (10) | 0.0422 (13) | −0.0005 (9) | 0.0004 (12) | 0.0018 (10) |
| C6 | 0.0521 (14) | 0.0604 (16) | 0.0390 (12) | −0.0001 (11) | 0.0008 (12) | 0.0009 (11) |
| C7 | 0.0365 (11) | 0.0509 (14) | 0.0441 (13) | 0.0051 (9) | −0.0047 (11) | −0.0113 (11) |
| C8 | 0.0568 (15) | 0.0671 (16) | 0.0645 (19) | 0.0018 (12) | −0.0065 (15) | −0.0243 (15) |
| O1—C1 | 1.232 (2) | C3—H3A | 0.9700 |
| N1—C1 | 1.320 (3) | C4—C5 | 1.490 (3) |
| N1—H1A | 0.8598 | C4—H4B | 0.9600 |
| N1—H1B | 0.8603 | C4—H4C | 0.9600 |
| N2—C5 | 1.347 (3) | C4—H4A | 0.9600 |
| N2—N3 | 1.359 (3) | C5—C6 | 1.373 (4) |
| N2—C3 | 1.448 (3) | C6—C7 | 1.394 (4) |
| N3—C7 | 1.335 (3) | C6—H6A | 0.9300 |
| C1—C2 | 1.505 (3) | C7—C8 | 1.488 (4) |
| C2—C3 | 1.518 (3) | C8—H8A | 0.9600 |
| C2—H2A | 0.9700 | C8—H8B | 0.9600 |
| C2—H2B | 0.9700 | C8—H8C | 0.9600 |
| C3—H3B | 0.9700 | ||
| C1—N1—H1A | 120.2 | C5—C4—H4B | 109.5 |
| C1—N1—H1B | 119.8 | C5—C4—H4C | 109.5 |
| H1A—N1—H1B | 120.0 | H4B—C4—H4C | 109.5 |
| C5—N2—N3 | 112.13 (18) | C5—C4—H4A | 109.5 |
| C5—N2—C3 | 129.18 (18) | H4B—C4—H4A | 109.5 |
| N3—N2—C3 | 118.66 (18) | H4C—C4—H4A | 109.5 |
| C7—N3—N2 | 104.88 (19) | N2—C5—C6 | 106.28 (19) |
| O1—C1—N1 | 122.5 (2) | N2—C5—C4 | 123.4 (2) |
| O1—C1—C2 | 121.3 (2) | C6—C5—C4 | 130.3 (2) |
| N1—C1—C2 | 116.14 (18) | C5—C6—C7 | 106.0 (2) |
| C1—C2—C3 | 113.56 (19) | C5—C6—H6A | 127.0 |
| C1—C2—H2A | 108.9 | C7—C6—H6A | 127.0 |
| C3—C2—H2A | 108.9 | N3—C7—C6 | 110.7 (2) |
| C1—C2—H2B | 108.9 | N3—C7—C8 | 120.2 (2) |
| C3—C2—H2B | 108.9 | C6—C7—C8 | 129.1 (3) |
| H2A—C2—H2B | 107.7 | C7—C8—H8A | 109.5 |
| N2—C3—C2 | 112.11 (19) | C7—C8—H8B | 109.5 |
| N2—C3—H3B | 109.2 | H8A—C8—H8B | 109.5 |
| C2—C3—H3B | 109.2 | C7—C8—H8C | 109.5 |
| N2—C3—H3A | 109.2 | H8A—C8—H8C | 109.5 |
| C2—C3—H3A | 109.2 | H8B—C8—H8C | 109.5 |
| H3B—C3—H3A | 107.9 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1i | 0.86 | 2.10 | 2.936 (3) | 164 |
| N1—H1B···N3ii | 0.86 | 2.30 | 3.084 (3) | 152 |
| C3—H3B···O1iii | 0.97 | 2.52 | 3.413 (3) | 154 |
| Symmetry codes: (i) x−1/4, −y+1/4, z−1/4; (ii) −x, −y, z; (iii) x+1/4, −y+1/4, z+1/4. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O1i | 0.86 | 2.10 | 2.936 (3) | 164 |
| N1—H1B···N3ii | 0.86 | 2.30 | 3.084 (3) | 152 |
| C3—H3B···O1iii | 0.97 | 2.52 | 3.413 (3) | 154 |
| Symmetry codes: (i) x−1/4, −y+1/4, z−1/4; (ii) −x, −y, z; (iii) x+1/4, −y+1/4, z+1/4. |
This project was sponsored by the K. C. Wong Magna Fund of Ningbo University and supported by the Project of Zhejiang Province Science and Technology Program (grant No. 2008 C21043), the Program of Ningbo Natural Science Foundation (grant No. 2007 A610053) and the Project of Zhejiang Province New Talent Program (grant No. 2008R40G2070020). We thank Ms Y. Zhou for the help with the structure analysis and Mr W. Xu for the diffraction data collection.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Mukherjee, R. (2000). Coord. Chem. Rev. 203, 151–218.
Pal, S., Barik, A. K., Gupta, S., Hazra, A., Kar, S. K., Peng, S. M., Lee, G. H., Butcher, R. J., Fallah, M. S. & Ribas, J. (2005). Inorg. Chem. 44, 3880–3889.
Paul, R. L., Argent, S. P., Jeffery, J. C., Harding, L. P., Lynamd, J. M. & Ward, M. D. (2004). Dalton Trans. pp. 3453–3458.
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.
Shaw, J. L., Garrison, S. A., Aleman, E. A., Ziegler, C. J. & Modarelli, D. A. (2004). J. Org. Chem. 69, 7423–7427.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
In recent years, there has been considerable interest in the use of hemilabile ligands containing substituted pyrazole groups because of their potential applications in catalysis and their ability for complex construction (Shaw et al., 2004; Pal et al., 2005). Nowadays, much attention has been focused on the design of various pyrazole ligands with special structural properties to fulfill the specific stereochemical requirement of a particular metal-binding site (Mukherjee, 2000; Paul et al., 2004). Herein, we report the crystal structure of the title compound. The molecluar structure of the title compound is shown in Fig. 1. In the crystal structure, molecules are linked by intermolecular N—H···N and N—H···O hydrogen bonds into a three dimensional network (see Fig. 2 and Table 1). Additional stabilization is provided by weak intermolecular C-H···O hydrogen bonds.