1-Allyl-3-amino-1H-pyrazole-4-carboxylic acid

Li, G.-C.; Wang, L.-Y.; Zhu, R.; Yang, F.-L.

doi:10.1107/S1600536808035538

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2264

doi:10.1107/S1600536808035538

Open

access

1-Allyl-3-amino-1H-pyrazole-4-carboxylic acid

Gong-Chun Li,^a Li-Ye Wang,^a Ran Zhu ^b and Feng-Ling Yang ^a ^*

^aCollege of Chemistry and Chemical Engineering, Xuchang University, Xuchang, Henan Province 461000, People's Republic of China, and ^bState Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, People's Republic of China
^*Correspondence e-mail: yfling2000cn@yahoo.com.cn

(Received 17 October 2008; accepted 30 October 2008; online 8 November 2008)

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—H⋯N and O—H⋯N).

Related literature

For details of the biological activities of pyrazole derivatives, see: Malhotra et al. (1997 ); Takao et al. (1994 ); Wang et al. (2005 ).

Experimental

Crystal data

C₇H₉N₃O₂
M_r = 167.17
Monoclinic, P 2₁ /c
a = 8.966 (2) Å
b = 8.531 (2) Å
c = 10.266 (2) Å
β = 95.57 (3)°
V = 781.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 113 (2) K
0.20 × 0.18 × 0.14 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.979, T_max = 0.985
5773 measured reflections
1852 independent reflections
1631 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.085
S = 1.06
1852 reflections
121 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.894 (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) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035538/lx2076sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035538/lx2076Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

For details of the biological activities of pyrazole derivatives, see: Malhotra et al. (1997); Takao et al. (1994); Wang et al., 2005).

Experimental top

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.

Computing details top

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).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.
	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.]

1-Allyl-3-amino-1H-pyrazole-4-carboxylic acid top

Crystal data top

C₇H₉N₃O₂	F(000) = 352
M_r = 167.17	D_x = 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

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1852 independent reflections
Radiation source: rotating anode	1631 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.025
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.9°, θ_min = 3.1°
ω and ϕ scans	h = −7→11
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −11→11
T_min = 0.979, T_max = 0.985	l = −13→13
5773 measured reflections

Refinement top

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(F_o²) + (0.0353P)² + 0.3376P] where P = (F_o² + 2F_c²)/3
1852 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₇H₉N₃O₂	V = 781.5 (3) Å³
M_r = 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)°

Data collection top

Rigaku Saturn CCD area-detector diffractometer	1852 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1631 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.985	R_int = 0.025
5773 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.29 e Å⁻³
1852 reflections	Δρ_min = −0.26 e Å⁻³
121 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Experimental details

Crystal data
Chemical formula	C₇H₉N₃O₂
M_r	167.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	113
a, b, c (Å)	8.966 (2), 8.531 (2), 10.266 (2)
β (°)	95.57 (3)
V (Å³)	781.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.18 × 0.14

Data collection
Diffractometer	Rigaku Saturn CCD area-detector diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.979, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	5773, 1852, 1631
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.085, 1.06
No. of reflections	1852
No. of parameters	121
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.26

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), CrystalStructure (Rigaku/MSC, 2005).

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

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).

References

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Malhotra, S., Parmar, V. S. & Errington, W. (1997). Acta Cryst. C53, 1885–1887. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Takao, H., Wakisaka, S. & Murai, K. (1994). Japanese Patent No. 06329633. Google Scholar
Wang, J.-G., Li, Z.-M., Ma, N., Wang, B.-L., Jiang, L., Pang, S.-S., Lee, Y.-T., Guddat, L. W. & Duggleby, R. G. (2005). J. Comput. Aided Mol. Des. 19, 801–820. Web of Science CrossRef PubMed CAS Google Scholar