3-[3-(2-Pyrid­yl)-1H-pyrazol-1-yl]propan­amide

Huang, F.; Jin, B.; Zhang, J.-F.

doi:10.1107/S1600536809019060

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1411

doi:10.1107/S1600536809019060

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3-[3-(2-Pyridyl)-1H-pyrazol-1-yl]propanamide

Feng Huang,^a Bin Jin ^a and Jian-Feng Zhang ^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 8 May 2009; accepted 20 May 2009; online 29 May 2009)

In the title compound, C₁₁H₁₂N₄O, the pyrazole and pyridine rings are nearly coplanar [dihedral angle = 1.87 (5)°]. Adjacent molecules are linked by N—H⋯N and N—H⋯O hydrogen bonds into a linear chain running along the c axis.

Related literature

For the chemistry of 3-(2-pyridyl)pyrazoles, see: Ruben et al. (2004 ); Steel (2005 ).

Experimental

Crystal data

C₁₁H₁₂N₄O
M_r = 216.25
Triclinic, $[P \overline 1]$
a = 7.7446 (15) Å
b = 8.3517 (17) Å
c = 8.4804 (17) Å
α = 97.99 (3)°
β = 98.95 (3)°
γ = 90.40 (3)°
V = 536.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.58 × 0.55 × 0.27 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.947, T_max = 0.972
5019 measured reflections
2410 independent reflections
1937 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.139
S = 1.12
2410 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.28 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	2.11	2.968 (2)	175
N1—H1B⋯N4ⁱⁱ	0.86	2.21	3.055 (2)	167
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, y, z-1.

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/S1600536809019060/ng2581sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019060/ng2581Isup2.hkl

checkCIF report

Comment top

Great attention has been paid to 3-(2-pyridyl)pyrazole-based ligands in the area of coordination chemistry, not only due to they can act as bridging or chelate ligands and their intriguing structures, but also for their potential applications as functional materials (Ruben et al., 2004; Steel et al., 2005). Herein, We report the structure of a N-Pyrazolylpropanamide ligand, C₁₁H₁₂N₄O (Scheme 1).

As is shown in Figure 1, in the title compound, the dihedral angle between pyrazole and pyridine ring is 1.87 (5)°, and the torsion angle of N3—C6—C7—N4 is 179.36 (2)°. The molecules are formed into a three-dimensional supermolecular network through intermolecular weak N—H···N (N···N= 3.055 (2) Å) and N—H···O (N···O= 2.968 (2) Å) hydrogen bonds (Figure 2).The hydrogen bond geometry parameters are list in Table 1. Weak π-π stacking interactions between pyrazole ring (N2/N3/C6/C5/C4) and pyridine ring (N4/C7/C8/C9/C10/C11) (symmetric code: -x, -y, 2 - z), with a centroid-to-centroid distance of 3.828 (1)Å and interplanar distance of 3.739 (1) Å, help to stabilize the crystal structure.

Related literature top

For the chemistry of 3-(2-pyridyl)pyrazoles, see: Ruben et al. (2004); Steel (2005).

Experimental top

A mixture of 3-(2-pyridyl)pyrazole (2.9 g, 20 mmol), sodium hydroxide (0.16 g, 4 mmol), N,N'-dimethylformamide(DMF)(100 ml) was stirred and heated to 373 k. A solution of acrylamide (1.44 g, 20 mmol) solubilized in DMF(10 ml)was added dropwise over a period of 10 minutes. After 7 h, heating was then terminated, and the solution was cooled to room temperature. The mixture was filtered, and DMF was removed by vacuum distillation. The product was then recrystallized from ethanol (yield: 64.7%; mp: 427 K). Calculated for C₁₁H₁₂N₄O: C 61.10, H 5.59, N 25.91%; found: C 60.03, H 5.48, N 25.86%.

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 45% probability level.
	Fig. 2. Partial packing view of the title compound. Dashed lines indicate N—H···N and N—H···O hydrogen bonds.

3-[3-(2-Pyridyl)-1H-pyrazol-1-yl]propanamide top

Crystal data top

C₁₁H₁₂N₄O	Z = 2
M_r = 216.25	F(000) = 228
Triclinic, P1	D_x = 1.339 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7446 (15) Å	Cell parameters from 5019 reflections
b = 8.3517 (17) Å	θ = 3.2–27.4°
c = 8.4804 (17) Å	µ = 0.09 mm⁻¹
α = 97.99 (3)°	T = 293 K
β = 98.95 (3)°	Block, colorless
γ = 90.40 (3)°	0.58 × 0.55 × 0.27 mm
V = 536.4 (2) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2410 independent reflections
Radiation source: fine-focus sealed tube	1937 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 0 pixels mm^-1	θ_max = 27.4°, θ_min = 3.2°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
T_min = 0.947, T_max = 0.972	l = −10→10
5019 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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.139	w = 1/[σ²(F_o²) + (0.0807P)² + 0.0265P] where P = (F_o² + 2F_c²)/3
S = 1.12	(Δ/σ)_max < 0.001
2410 reflections	Δρ_max = 0.37 e Å⁻³
146 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.038 (11)

Crystal data top

C₁₁H₁₂N₄O	γ = 90.40 (3)°
M_r = 216.25	V = 536.4 (2) Å³
Triclinic, P1	Z = 2
a = 7.7446 (15) Å	Mo Kα radiation
b = 8.3517 (17) Å	µ = 0.09 mm⁻¹
c = 8.4804 (17) Å	T = 293 K
α = 97.99 (3)°	0.58 × 0.55 × 0.27 mm
β = 98.95 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2410 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1937 reflections with I > 2σ(I)
T_min = 0.947, T_max = 0.972	R_int = 0.029
5019 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.12	Δρ_max = 0.37 e Å⁻³
2410 reflections	Δρ_min = −0.28 e Å⁻³
146 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
N1	0.41230 (16)	0.30020 (14)	0.39463 (14)	0.0502 (3)
H1A	0.5037	0.3623	0.4058	0.060*
H1B	0.4039	0.2110	0.3293	0.060*
O1	0.28772 (12)	0.46829 (11)	0.57395 (12)	0.0495 (3)
C1	0.28366 (17)	0.34222 (15)	0.47849 (14)	0.0391 (3)
C2	0.13022 (19)	0.22241 (18)	0.44677 (16)	0.0509 (4)
H2A	0.0683	0.2257	0.3387	0.061*
H2B	0.1748	0.1145	0.4503	0.061*
C3	0.00195 (18)	0.25207 (18)	0.56416 (17)	0.0477 (4)
H3A	−0.0373	0.3623	0.5664	0.057*
H3B	−0.0994	0.1801	0.5266	0.057*
N2	0.07610 (14)	0.22676 (13)	0.72718 (13)	0.0403 (3)
C4	0.0879 (2)	0.33312 (17)	0.86282 (18)	0.0500 (4)
H4A	0.0518	0.4395	0.8703	0.060*
C5	0.1622 (2)	0.25694 (17)	0.98736 (17)	0.0496 (4)
H5A	0.1874	0.2996	1.0959	0.060*
C6	0.19232 (15)	0.09985 (15)	0.91577 (15)	0.0367 (3)
N3	0.13956 (14)	0.08220 (13)	0.75618 (13)	0.0401 (3)
C7	0.26942 (15)	−0.03550 (14)	0.99317 (15)	0.0368 (3)
C8	0.28816 (18)	−0.18581 (16)	0.90392 (18)	0.0457 (3)
H8A	0.2547	−0.2021	0.7926	0.055*
C9	0.3569 (2)	−0.30988 (17)	0.9829 (2)	0.0555 (4)
H9A	0.3706	−0.4110	0.9253	0.067*
C10	0.4054 (2)	−0.28298 (19)	1.1479 (2)	0.0576 (4)
H10A	0.4498	−0.3655	1.2041	0.069*
C11	0.3862 (2)	−0.13031 (19)	1.22693 (19)	0.0538 (4)
H11A	0.4210	−0.1116	1.3381	0.065*
N4	0.32045 (15)	−0.00708 (14)	1.15354 (14)	0.0451 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0535 (7)	0.0437 (6)	0.0500 (7)	−0.0114 (5)	0.0099 (5)	−0.0069 (5)
O1	0.0528 (6)	0.0395 (5)	0.0531 (6)	−0.0070 (4)	0.0085 (5)	−0.0038 (4)
C1	0.0461 (7)	0.0361 (6)	0.0327 (6)	−0.0044 (5)	−0.0025 (5)	0.0070 (5)
C2	0.0590 (9)	0.0539 (8)	0.0366 (7)	−0.0193 (7)	0.0031 (6)	0.0012 (6)
C3	0.0437 (7)	0.0515 (8)	0.0466 (8)	−0.0067 (6)	−0.0011 (6)	0.0121 (6)
N2	0.0428 (6)	0.0378 (6)	0.0409 (6)	0.0012 (4)	0.0078 (4)	0.0057 (4)
C4	0.0662 (9)	0.0374 (7)	0.0486 (8)	0.0102 (6)	0.0171 (7)	0.0040 (6)
C5	0.0715 (9)	0.0410 (7)	0.0364 (7)	0.0097 (6)	0.0124 (6)	0.0007 (5)
C6	0.0361 (6)	0.0354 (6)	0.0389 (7)	−0.0020 (5)	0.0092 (5)	0.0028 (5)
N3	0.0408 (6)	0.0356 (5)	0.0421 (6)	−0.0008 (4)	0.0037 (4)	0.0019 (4)
C7	0.0326 (6)	0.0358 (6)	0.0418 (7)	−0.0022 (5)	0.0071 (5)	0.0031 (5)
C8	0.0439 (7)	0.0412 (7)	0.0479 (8)	0.0025 (5)	0.0031 (6)	−0.0025 (6)
C9	0.0539 (8)	0.0384 (7)	0.0704 (10)	0.0086 (6)	0.0045 (7)	−0.0001 (7)
C10	0.0580 (9)	0.0467 (8)	0.0698 (11)	0.0122 (7)	0.0072 (7)	0.0175 (7)
C11	0.0603 (9)	0.0545 (8)	0.0469 (8)	0.0079 (7)	0.0048 (6)	0.0120 (7)
N4	0.0515 (7)	0.0417 (6)	0.0417 (6)	0.0033 (5)	0.0072 (5)	0.0041 (5)

Geometric parameters (Å, º) top

N1—C1	1.3332 (18)	C5—C6	1.4040 (18)
N1—H1A	0.8600	C5—H5A	0.9300
N1—H1B	0.8600	C6—N3	1.3386 (16)
O1—C1	1.2328 (16)	C6—C7	1.4693 (18)
C1—C2	1.5150 (18)	C7—N4	1.3431 (18)
C2—C3	1.511 (2)	C7—C8	1.3938 (19)
C2—H2A	0.9700	C8—C9	1.377 (2)
C2—H2B	0.9700	C8—H8A	0.9300
C3—N2	1.4566 (18)	C9—C10	1.378 (2)
C3—H3A	0.9700	C9—H9A	0.9300
C3—H3B	0.9700	C10—C11	1.376 (2)
N2—C4	1.3427 (19)	C10—H10A	0.9300
N2—N3	1.3464 (16)	C11—N4	1.3389 (19)
C4—C5	1.362 (2)	C11—H11A	0.9300
C4—H4A	0.9300

C1—N1—H1A	120.0	C4—C5—C6	104.82 (13)
C1—N1—H1B	120.0	C4—C5—H5A	127.6
H1A—N1—H1B	120.0	C6—C5—H5A	127.6
O1—C1—N1	123.19 (12)	N3—C6—C5	110.81 (12)
O1—C1—C2	122.26 (12)	N3—C6—C7	120.56 (11)
N1—C1—C2	114.55 (11)	C5—C6—C7	128.63 (12)
C3—C2—C1	114.53 (11)	C6—N3—N2	104.84 (10)
C3—C2—H2A	108.6	N4—C7—C8	121.89 (13)
C1—C2—H2A	108.6	N4—C7—C6	116.74 (11)
C3—C2—H2B	108.6	C8—C7—C6	121.38 (12)
C1—C2—H2B	108.6	C9—C8—C7	119.08 (14)
H2A—C2—H2B	107.6	C9—C8—H8A	120.5
N2—C3—C2	112.93 (12)	C7—C8—H8A	120.5
N2—C3—H3A	109.0	C8—C9—C10	119.41 (14)
C2—C3—H3A	109.0	C8—C9—H9A	120.3
N2—C3—H3B	109.0	C10—C9—H9A	120.3
C2—C3—H3B	109.0	C11—C10—C9	118.01 (15)
H3A—C3—H3B	107.8	C11—C10—H10A	121.0
C4—N2—N3	111.95 (11)	C9—C10—H10A	121.0
C4—N2—C3	127.56 (12)	N4—C11—C10	123.96 (15)
N3—N2—C3	120.47 (11)	N4—C11—H11A	118.0
N2—C4—C5	107.59 (13)	C10—C11—H11A	118.0
N2—C4—H4A	126.2	C11—N4—C7	117.61 (12)
C5—C4—H4A	126.2

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.86	2.11	2.968 (2)	175
N1—H1B···N4ⁱⁱ	0.86	2.21	3.055 (2)	167

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂N₄O
M_r	216.25
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.7446 (15), 8.3517 (17), 8.4804 (17)
α, β, γ (°)	97.99 (3), 98.95 (3), 90.40 (3)
V (Å³)	536.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.58 × 0.55 × 0.27

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.947, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	5019, 2410, 1937
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.139, 1.12
No. of reflections	2410
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.28

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	2.11	2.968 (2)	175
N1—H1B···N4ⁱⁱ	0.86	2.21	3.055 (2)	167

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z−1.

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) and Programs of the Ningbo Natural Science Foundation (grant No.2007 A610053). We thank Ms H.-L. Zhu and Y. Zhou for their help with the structure analysis and Mr W. Xu for the data collection.

References

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