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

Zhang, J.-F.; Huang, F.; Chen, S.-J.

doi:10.1107/S160053680903342X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2442

doi:10.1107/S160053680903342X

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

Jian-Feng Zhang,^a ^* Feng Huang ^a and Shu-Jiao Chen ^a

^aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang 315211, People's Republic of China
^*Correspondence e-mail: zjf@nbu.edu.cn

(Received 12 June 2009; accepted 21 August 2009; online 12 September 2009)

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 ); Shaw et al. (2004 ). 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 ); Paul et al. (2004 );

Experimental

Crystal data

C₈H₁₃N₃O
M_r = 167.21
Orthorhombic, F d d 2
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 ) 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[F² > 2σ(F²)] = 0.033
wR(F²) = 0.093
S = 1.14
1067 reflections
112 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[x-{\script{1\over 4}}, -y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (ii) -x, -y, z; (iii) $[x+{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; 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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

For the potential applications of hemilabile ligands containing substituted pyrazole groups, see: Pal et al. (2005); Shaw et al. (2004). 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); Paul et al. (2004);

Experimental top

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%.

Computing details top

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).

Figures top

	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.

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

Crystal data top

C₈H₁₃N₃O	F(000) = 1440
M_r = 167.21	D_x = 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

Data collection top

Rigaku R-AXIS RAPID diffractometer	1067 independent reflections
Radiation source: fine-focus sealed tube	890 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 0 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −17→18
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −43→43
T_min = 0.963, T_max = 0.970	l = −9→8
4623 measured reflections

Refinement top

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(F_o²) + (0.0446P)² + 1.8694P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max < 0.001
1067 reflections	Δρ_max = 0.14 e Å⁻³
112 parameters	Δρ_min = −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)

Crystal data top

C₈H₁₃N₃O	V = 3588.0 (16) Å³
M_r = 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

Data collection top

Rigaku R-AXIS RAPID diffractometer	1067 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	890 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.970	R_int = 0.044
4623 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	1 restraint
wR(F²) = 0.093	H-atom parameters constrained
S = 1.14	Δρ_max = 0.14 e Å⁻³
1067 reflections	Δρ_min = −0.19 e Å⁻³
112 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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.

Experimental details

Crystal data
Chemical formula	C₈H₁₃N₃O
M_r	167.21
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	298
a, b, c (Å)	14.452 (5), 33.390 (7), 7.4354 (15)
V (Å³)	3588.0 (16)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.47 × 0.37 × 0.36

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.963, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	4623, 1067, 890
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.093, 1.14
No. of reflections	1067
No. of parameters	112
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.19

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

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.

References

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