5-Amino-1-phenyl-1H-pyrazole-4-carboxylic acid.

In the mol-ecule of the title compound, C(10)H(9)N(3)O(2), the pyrazole ring is approximately coplanar with the amino and carboxyl groups. The phenyl group is twisted by 48.13 (3)° relative to this plane. An intra-molecular N-H⋯O hydrogen bond stabilizes the planar conformation of the mol-ecule. The mol-ecules are linked into two-dimensional sheets by two strong inter-molecular N-H⋯N and O-H⋯O hydrogen bonds. The latter forms the classic carboxylic acid dimer motif.

Related literature

For related literature, see: Baroni & Kovyrzina (1961 ▶); Baraldi et al. (1998 ▶); Bruno et al. (1990 ▶); Chen & Li (1998 ▶); Cottineau et al. (2002 ▶); Dardari et al. (2006 ▶); Jin et al. (2004 ▶); Li et al. (2006 ▶); Londershausen (1996 ▶); Mishra et al. (1998 ▶); Neunhoeffer et al. (1959 ▶); Siddiqui et al. (2007 ▶); Smith et al. (2001 ▶); Zhong et al. (2006 ▶); Zia-ur-Rehman et al. (2005 ▶, 2006 ▶).

Experimental

Crystal data

C10H9N3O2

M = 203.20

Monoclinic,

a = 3.7937 (5) Å

b = 21.613 (3) Å

c = 11.1580 (16) Å

β = 92.170 (2)°

V = 914.2 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 150 (2) K

0.28 × 0.10 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.971, T max = 0.993

10482 measured reflections

2800 independent reflections

1967 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.116

S = 1.02

2800 reflections

145 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; 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: SHELXTL and local programs.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018394/bt2722sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018394/bt2722Isup2.hkl

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

C10H9N3O2	F000 = 424
Mr = 203.20	Dx = 1.476 Mg m−3
Monoclinic, P21/n	Melting point: 460 K
Hall symbol: -P 2yn	Mo Kα radiation λ = 0.71073 Å
a = 3.7937 (5) Å	Cell parameters from 2299 reflections
b = 21.613 (3) Å	θ = 3.4–29.6º
c = 11.1580 (16) Å	µ = 0.11 mm−1
β = 92.170 (2)º	T = 150 (2) K
V = 914.2 (2) Å3	Block, colourless
Z = 4	0.28 × 0.10 × 0.07 mm

Bruker APEXII CCD diffractometer	2800 independent reflections
Radiation source: fine-focus sealed tube	1967 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.034
T = 150(2) K	θmax = 30.6º
ω rotation with narrow frames scans	θmin = 1.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 2007)	h = −5→5
Tmin = 0.971, Tmax = 0.993	k = −30→30
10482 measured reflections	l = −15→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom except NH & OH coords freely refined
R[F2 > 2σ(F2)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116	w = 1/[σ2(Fo2) + (0.0521P)2 + 0.3077P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2800 reflections	Δρmax = 0.34 e Å−3
145 parameters	Δρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
C1	0.0569 (4)	0.34024 (6)	−0.20989 (12)	0.0196 (3)
H1	−0.0345	0.3206	−0.2807	0.023*
C2	0.0428 (4)	0.40410 (7)	−0.19887 (13)	0.0242 (3)
H2	−0.0548	0.4284	−0.2628	0.029*
C3	0.1711 (4)	0.43247 (7)	−0.09461 (14)	0.0262 (3)
H3	0.1623	0.4762	−0.0873	0.031*
C4	0.3122 (4)	0.39693 (7)	−0.00110 (13)	0.0235 (3)
H4C	0.3958	0.4165	0.0707	0.028*
C5	0.3323 (4)	0.33300 (6)	−0.01161 (12)	0.0196 (3)
H5	0.4313	0.3087	0.0522	0.024*
C6	0.2054 (3)	0.30513 (6)	−0.11682 (11)	0.0168 (3)
N2	0.2312 (3)	0.23989 (5)	−0.13188 (9)	0.0172 (2)
N3	0.3587 (3)	0.21589 (5)	−0.23810 (10)	0.0205 (3)
C7	0.3374 (4)	0.15556 (6)	−0.22523 (12)	0.0200 (3)
H7	0.4084	0.1268	−0.2839	0.024*
C8	0.1976 (4)	0.13829 (6)	−0.11488 (11)	0.0175 (3)
C9	0.1300 (3)	0.19438 (6)	−0.05734 (11)	0.0163 (3)
N4	−0.0209 (3)	0.20277 (6)	0.04849 (10)	0.0221 (3)
H4A	−0.068 (5)	0.1668 (8)	0.0857 (15)	0.027*
H4B	−0.028 (5)	0.2377 (8)	0.0881 (16)	0.027*
C10	0.1212 (4)	0.07860 (6)	−0.06630 (12)	0.0198 (3)
O3	−0.0099 (3)	0.07239 (4)	0.03332 (9)	0.0247 (2)
O4	0.1962 (3)	0.03107 (5)	−0.13546 (9)	0.0289 (3)
H4	0.132 (5)	−0.0050 (10)	−0.0983 (17)	0.043*

	U11	U22	U33	U12	U13	U23
C1	0.0207 (7)	0.0229 (7)	0.0153 (6)	0.0004 (5)	0.0039 (5)	0.0023 (5)
C2	0.0263 (7)	0.0229 (7)	0.0239 (7)	0.0054 (6)	0.0068 (6)	0.0071 (5)
C3	0.0298 (8)	0.0172 (6)	0.0324 (8)	−0.0002 (6)	0.0113 (6)	−0.0003 (5)
C4	0.0257 (7)	0.0229 (7)	0.0222 (7)	−0.0043 (5)	0.0052 (5)	−0.0049 (5)
C5	0.0210 (7)	0.0208 (6)	0.0171 (6)	−0.0009 (5)	0.0011 (5)	−0.0005 (5)
C6	0.0183 (6)	0.0163 (6)	0.0161 (6)	−0.0002 (5)	0.0046 (5)	0.0009 (5)
N2	0.0238 (6)	0.0162 (5)	0.0119 (5)	−0.0004 (4)	0.0040 (4)	0.0001 (4)
N3	0.0285 (6)	0.0208 (6)	0.0126 (5)	0.0010 (5)	0.0069 (4)	−0.0007 (4)
C7	0.0266 (7)	0.0192 (6)	0.0144 (6)	0.0006 (5)	0.0042 (5)	−0.0011 (5)
C8	0.0227 (6)	0.0164 (6)	0.0136 (6)	−0.0001 (5)	0.0029 (5)	0.0000 (4)
C9	0.0195 (6)	0.0164 (6)	0.0133 (6)	−0.0004 (5)	0.0013 (5)	0.0009 (4)
N4	0.0348 (7)	0.0168 (5)	0.0153 (5)	−0.0022 (5)	0.0095 (5)	−0.0009 (4)
C10	0.0256 (7)	0.0173 (6)	0.0165 (6)	−0.0001 (5)	0.0034 (5)	−0.0009 (5)
O3	0.0384 (6)	0.0179 (5)	0.0185 (5)	−0.0016 (4)	0.0096 (4)	0.0006 (4)
O4	0.0493 (7)	0.0158 (5)	0.0228 (5)	−0.0021 (5)	0.0157 (5)	−0.0022 (4)

C1—C2	1.387 (2)	N2—N3	1.3968 (15)
C1—C6	1.3883 (18)	N3—C7	1.3146 (18)
C1—H1	0.9500	C7—C8	1.4092 (17)
C2—C3	1.387 (2)	C7—H7	0.9500
C2—H2	0.9500	C8—C9	1.4001 (17)
C3—C4	1.387 (2)	C8—C10	1.4331 (18)
C3—H3	0.9500	C9—N4	1.3438 (16)
C4—C5	1.3891 (19)	N4—H4A	0.903 (18)
C4—H4C	0.9500	N4—H4B	0.876 (18)
C5—C6	1.3891 (18)	C10—O3	1.2423 (16)
C5—H5	0.9500	C10—O4	1.3221 (16)
C6—N2	1.4239 (16)	O4—H4	0.92 (2)
N2—C9	1.3530 (16)
C2—C1—C6	119.58 (13)	C9—N2—C6	128.69 (11)
C2—C1—H1	120.2	N3—N2—C6	119.69 (10)
C6—C1—H1	120.2	C7—N3—N2	104.53 (10)
C3—C2—C1	120.06 (13)	N3—C7—C8	112.64 (12)
C3—C2—H2	120.0	N3—C7—H7	123.7
C1—C2—H2	120.0	C8—C7—H7	123.7
C4—C3—C2	119.97 (13)	C9—C8—C7	104.64 (11)
C4—C3—H3	120.0	C9—C8—C10	124.25 (12)
C2—C3—H3	120.0	C7—C8—C10	131.08 (12)
C3—C4—C5	120.55 (13)	N4—C9—N2	125.61 (12)
C3—C4—H4C	119.7	N4—C9—C8	127.68 (12)
C5—C4—H4C	119.7	N2—C9—C8	106.64 (11)
C4—C5—C6	118.97 (13)	C9—N4—H4A	112.7 (11)
C4—C5—H5	120.5	C9—N4—H4B	125.6 (11)
C6—C5—H5	120.5	H4A—N4—H4B	120.0 (16)
C1—C6—C5	120.86 (13)	O3—C10—O4	122.72 (12)
C1—C6—N2	118.73 (12)	O3—C10—C8	121.96 (12)
C5—C6—N2	120.40 (12)	O4—C10—C8	115.31 (12)
C9—N2—N3	111.54 (10)	C10—O4—H4	109.2 (12)
C6—C1—C2—C3	−1.1 (2)	N3—C7—C8—C9	0.05 (16)
C1—C2—C3—C4	−0.3 (2)	N3—C7—C8—C10	178.11 (14)
C2—C3—C4—C5	1.2 (2)	N3—N2—C9—N4	−176.22 (12)
C3—C4—C5—C6	−0.7 (2)	C6—N2—C9—N4	0.3 (2)
C2—C1—C6—C5	1.6 (2)	N3—N2—C9—C8	0.98 (15)
C2—C1—C6—N2	−177.34 (12)	C6—N2—C9—C8	177.55 (13)
C4—C5—C6—C1	−0.7 (2)	C7—C8—C9—N4	176.51 (14)
C4—C5—C6—N2	178.20 (12)	C10—C8—C9—N4	−1.7 (2)
C1—C6—N2—C9	−130.01 (14)	C7—C8—C9—N2	−0.62 (15)
C5—C6—N2—C9	51.1 (2)	C10—C8—C9—N2	−178.85 (13)
C1—C6—N2—N3	46.33 (17)	C9—C8—C10—O3	−0.8 (2)
C5—C6—N2—N3	−132.62 (13)	C7—C8—C10—O3	−178.56 (14)
C9—N2—N3—C7	−0.93 (15)	C9—C8—C10—O4	178.38 (13)
C6—N2—N3—C7	−177.85 (12)	C7—C8—C10—O4	0.7 (2)
N2—N3—C7—C8	0.51 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O3	0.903 (18)	2.136 (18)	2.8233 (16)	132.3 (14)
N4—H4B···N3i	0.876 (18)	2.239 (18)	3.0087 (17)	146.5 (15)
O4—H4···O3ii	0.92 (2)	1.70 (2)	2.6189 (14)	178.4 (19)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O3	0.903 (18)	2.136 (18)	2.8233 (16)	132.3 (14)
N4—H4B⋯N3i	0.876 (18)	2.239 (18)	3.0087 (17)	146.5 (15)
O4—H4⋯O3ii	0.92 (2)	1.70 (2)	2.6189 (14)	178.4 (19)

Symmetry codes: (i) ; (ii) .