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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2442.
Published online 2009 September 12. doi:  10.1107/S160053680903342X
PMCID: PMC2970388

3-(3,5-Dimethyl-1H-pyrazol-1-yl)propanamide

Abstract

In the crystal of the title compound, C8H13N3O, mol­ecules are linked by inter­molecular N—H(...)N and N—H(...)O hydrogen bonds into a three-dimensional network. Additional stabilization is provided by weak inter­molecular C—H(...)O hydrogen bonds.

Related literature

For the potential applications of hemilabile ligands containing substituted pyrazole groups, see: Pal et al. (2005 [triangle]); Shaw et al. (2004 [triangle]). For the design of various pyrazole ligands with special structural properties to fulfill the specific stereochemical requirement of a particular metal-binding site, see: Mukherjee (2000 [triangle]); Paul et al. (2004 [triangle]);

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Object name is e-65-o2442-scheme1.jpg

Experimental

Crystal data

  • C8H13N3O
  • M r = 167.21
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2442-efi1.jpg
  • a = 14.452 (5) Å
  • b = 33.390 (7) Å
  • c = 7.4354 (15) Å
  • V = 3588.0 (16) Å3
  • Z = 16
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 298 K
  • 0.47 × 0.37 × 0.36 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.963, T max = 0.970
  • 4623 measured reflections
  • 1067 independent reflections
  • 890 reflections with I > 2σ(I)
  • R int = 0.044

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.093
  • S = 1.14
  • 1067 reflections
  • 112 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.19 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903342X/lh2847sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903342X/lh2847Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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%.

Refinement

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.

Figures

Fig. 1.
The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
Part of the crystal structure of the title compound. Dashed lines indicate hydrogen bonds.

Crystal data

C8H13N3OF(000) = 1440
Mr = 167.21Dx = 1.238 Mg m3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 4623 reflections
a = 14.452 (5) Åθ = 3.1–27.5°
b = 33.390 (7) ŵ = 0.09 mm1
c = 7.4354 (15) ÅT = 298 K
V = 3588.0 (16) Å3Block, colorless
Z = 160.47 × 0.37 × 0.36 mm

Data collection

Rigaku R-AXIS RAPID diffractometer1067 independent reflections
Radiation source: fine-focus sealed tube890 reflections with I > 2σ(I)
graphiteRint = 0.044
Detector resolution: 0 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = −17→18
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)k = −43→43
Tmin = 0.963, Tmax = 0.970l = −9→8
4623 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033H-atom parameters constrained
wR(F2) = 0.093w = 1/[σ2(Fo2) + (0.0446P)2 + 1.8694P] where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max < 0.001
1067 reflectionsΔρmax = 0.14 e Å3
112 parametersΔρmin = −0.19 e Å3
1 restraintExtinction correction: SHELXTL'(Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0108 (8)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.02008 (12)0.12376 (4)0.3335 (3)0.0530 (5)
N1−0.08464 (14)0.07777 (6)0.2532 (4)0.0530 (6)
H1A−0.11850.09520.19910.064*
H1B−0.10130.05300.25560.064*
N20.15555 (13)0.04420 (5)0.1786 (2)0.0364 (5)
N30.12698 (13)0.00771 (5)0.1195 (3)0.0413 (5)
C1−0.00707 (15)0.08880 (6)0.3326 (3)0.0380 (5)
C20.04624 (16)0.05620 (6)0.4265 (3)0.0435 (6)
H2A0.01630.03070.40320.052*
H2B0.04410.06090.55510.052*
C30.14666 (15)0.05349 (7)0.3680 (3)0.0391 (5)
H3B0.17710.07880.39240.047*
H3A0.17750.03290.43790.047*
C40.2226 (2)0.10885 (7)0.0702 (5)0.0622 (8)
H4B0.27460.10820.15040.093*
H4C0.17470.12530.12100.093*
H4A0.24140.1198−0.04340.093*
C50.18687 (15)0.06742 (6)0.0435 (3)0.0422 (5)
C60.17798 (19)0.04516 (8)−0.1109 (4)0.0505 (6)
H6A0.19380.0529−0.22700.061*
C70.14038 (16)0.00856 (7)−0.0582 (3)0.0438 (6)
C80.1147 (2)−0.02660 (9)−0.1705 (5)0.0628 (8)
H8A0.1465−0.0499−0.12740.094*
H8B0.1319−0.0217−0.29320.094*
H8C0.0491−0.0309−0.16340.094*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0548 (10)0.0323 (7)0.0719 (13)−0.0018 (6)−0.0196 (10)−0.0002 (8)
N10.0488 (10)0.0381 (9)0.0720 (16)−0.0038 (8)−0.0163 (12)0.0039 (11)
N20.0386 (10)0.0338 (10)0.0369 (10)0.0008 (7)−0.0009 (9)−0.0020 (8)
N30.0410 (10)0.0342 (9)0.0486 (12)0.0007 (7)−0.0011 (10)−0.0057 (8)
C10.0391 (11)0.0335 (9)0.0415 (12)0.0025 (8)0.0025 (10)−0.0037 (9)
C20.0473 (13)0.0385 (11)0.0447 (13)0.0024 (9)0.0045 (11)0.0049 (10)
C30.0419 (12)0.0367 (10)0.0387 (12)0.0061 (9)−0.0027 (11)−0.0005 (9)
C40.0787 (19)0.0442 (13)0.0636 (18)−0.0134 (12)0.0057 (17)0.0057 (13)
C50.0425 (11)0.0419 (10)0.0422 (13)−0.0005 (9)0.0004 (12)0.0018 (10)
C60.0521 (14)0.0604 (16)0.0390 (12)−0.0001 (11)0.0008 (12)0.0009 (11)
C70.0365 (11)0.0509 (14)0.0441 (13)0.0051 (9)−0.0047 (11)−0.0113 (11)
C80.0568 (15)0.0671 (16)0.0645 (19)0.0018 (12)−0.0065 (15)−0.0243 (15)

Geometric parameters (Å, °)

O1—C11.232 (2)C3—H3A0.9700
N1—C11.320 (3)C4—C51.490 (3)
N1—H1A0.8598C4—H4B0.9600
N1—H1B0.8603C4—H4C0.9600
N2—C51.347 (3)C4—H4A0.9600
N2—N31.359 (3)C5—C61.373 (4)
N2—C31.448 (3)C6—C71.394 (4)
N3—C71.335 (3)C6—H6A0.9300
C1—C21.505 (3)C7—C81.488 (4)
C2—C31.518 (3)C8—H8A0.9600
C2—H2A0.9700C8—H8B0.9600
C2—H2B0.9700C8—H8C0.9600
C3—H3B0.9700
C1—N1—H1A120.2C5—C4—H4B109.5
C1—N1—H1B119.8C5—C4—H4C109.5
H1A—N1—H1B120.0H4B—C4—H4C109.5
C5—N2—N3112.13 (18)C5—C4—H4A109.5
C5—N2—C3129.18 (18)H4B—C4—H4A109.5
N3—N2—C3118.66 (18)H4C—C4—H4A109.5
C7—N3—N2104.88 (19)N2—C5—C6106.28 (19)
O1—C1—N1122.5 (2)N2—C5—C4123.4 (2)
O1—C1—C2121.3 (2)C6—C5—C4130.3 (2)
N1—C1—C2116.14 (18)C5—C6—C7106.0 (2)
C1—C2—C3113.56 (19)C5—C6—H6A127.0
C1—C2—H2A108.9C7—C6—H6A127.0
C3—C2—H2A108.9N3—C7—C6110.7 (2)
C1—C2—H2B108.9N3—C7—C8120.2 (2)
C3—C2—H2B108.9C6—C7—C8129.1 (3)
H2A—C2—H2B107.7C7—C8—H8A109.5
N2—C3—C2112.11 (19)C7—C8—H8B109.5
N2—C3—H3B109.2H8A—C8—H8B109.5
C2—C3—H3B109.2C7—C8—H8C109.5
N2—C3—H3A109.2H8A—C8—H8C109.5
C2—C3—H3A109.2H8B—C8—H8C109.5
H3B—C3—H3A107.9

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.862.102.936 (3)164
N1—H1B···N3ii0.862.303.084 (3)152
C3—H3B···O1iii0.972.523.413 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2847).

References

  • 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. [PubMed]
  • Paul, R. L., Argent, S. P., Jeffery, J. C., Harding, L. P., Lynamd, J. M. & Ward, M. D. (2004). Dalton Trans pp. 3453–3458. [PubMed]
  • 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. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography