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

The title compound, C(7)H(9)N(3)O(2), was prepared by alkaline hydrolysis of ethyl 1-allyl-3-amino-1H-pyrazole-4-carboxyl-ate. The crystal structure is stabilized by three types of inter-molecular 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 = 167.17

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.085

S = 1.06

1852 reflections

121 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.26 e Å−3

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 ▶).

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

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

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

C7H9N3O2	F000 = 352
Mr = 167.17	Dx = 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 = 2.4–27.9º
b = 8.531 (2) Å	µ = 0.11 mm−1
c = 10.266 (2) Å	T = 113 (2) K
β = 95.57 (3)º	Prism, colorless
V = 781.5 (3) Å3	0.20 × 0.18 × 0.14 mm
Z = 4

Rigaku Saturn CCD area-detector diffractometer	1852 independent reflections
Radiation source: rotating anode	1631 reflections with I > 2σ(I)
Monochromator: confocal	Rint = 0.025
Detector resolution: 7.31 pixels mm-1	θmax = 27.9º
T = 113(2) K	θmin = 3.1º
ω and φ scans	h = −7→11
Absorption correction: Multi-scan(CrystalClear; Rigaku/MSC, 2005)	k = −11→11
Tmin = 0.979, Tmax = 0.985	l = −13→13
5773 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)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.085	w = 1/[σ2(Fo2) + (0.0353P)2 + 0.3376P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1852 reflections	Δρmax = 0.29 e Å−3
121 parameters	Δρmin = −0.25 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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)

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) ; (ii) ; (iii) .