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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1312–o1313.
Published online 2008 June 21. doi:  10.1107/S1600536808018394
PMCID: PMC2961688

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

Abstract

In the mol­ecule of the title compound, C10H9N3O2, 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 intra­molecular N—H(...)O hydrogen bond stabilizes the planar conformation of the mol­ecule. The mol­ecules are linked into two-dimensional sheets by two strong inter­molecular 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 [triangle]); Baraldi et al. (1998 [triangle]); Bruno et al. (1990 [triangle]); Chen & Li (1998 [triangle]); Cottineau et al. (2002 [triangle]); Dardari et al. (2006 [triangle]); Jin et al. (2004 [triangle]); Li et al. (2006 [triangle]); Londershausen (1996 [triangle]); Mishra et al. (1998 [triangle]); Neunhoeffer et al. (1959 [triangle]); Siddiqui et al. (2007 [triangle]); Smith et al. (2001 [triangle]); Zhong et al. (2006 [triangle]); Zia-ur-Rehman et al. (2005 [triangle], 2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1312-scheme1.jpg

Experimental

Crystal data

  • C10H9N3O2
  • M r = 203.20
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1312-efi1.jpg
  • 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 [triangle]) 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 [triangle]); cell refinement: SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL and local programs.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

The authors are grateful to the Pakistan Council of Scientific and Industrial Research Laboratories Complex, Lahore, for the provision of necessary chemicals.

supplementary crystallographic information

Comment

Pyrazole and its derivatives are known as heterocyclic compounds, having a wide range of biological activities. Some pyrazoles have been reported to possess significant antiarrhythmic and sedative (Bruno et al., 1990), hypoglycemic (Cottineau et al., 2002), antiviral (Baraldi et al., 1998), and pesticidal (Londershausen,1996) activities. Some of their derivatives have also been successfully tested for their antifungal (Chen & Li, 1998), antihistaminic (Mishra et al., 1998) and anti-inflammatory (Smith et al., 2001) activities. In addition, they have also been used as ligands to investigate the structure–activity relationship of the active site of metalloproteins (Dardari et al., 2006) and for the preparation of some commercially important dyestuffs (Baroni & Kovyrzina, 1961; Neunhoeffer et al., 1959).

As part of our ongoing research on the synthesis and biological evaluation of heterocyclic compounds (Zia-ur-Rehman et al., 2005, 2006; Siddiqui et al., 2007), the crystal structure of the title compound, (I), was determined. In (I), the pyrazole ring is approximately co-planar with the amino and carboxylic acid groups. The C—N bond lengths in the pyrazole ring are 1.3146 (18) and 1.3530 (16) Å, which are shorter than a typical C—N single bond length of 1.443 Å, but longer than a typical C—N bond length of 1.269 Å (Jin et al., 2004), indicating electron delocalization. Most of the bond lengths and angles in N-phenylpyrazole group are in consistent with those in similar molecules (Li et al., 2006; Zhong et al., 2006). Each molecule exhibits an intramolecular N—H···O hydrogen bond which stabilizes the planar conformation and is linked to an adjacent one through head-to-tail pairs of O—H···O intermolecular interactions giving rise to dimeric motifs typical for carboxylic acids. Neighbouring dimers are further arranged into two-dimensional sheets in the (101) plane through N—H···N interactions (Fig.2).

Experimental

A mixture of 5-amino-1-phenyl-1H-pyrazole-4-carboxylic acid, ethyl ester (2.312 g; 10.0 mmoles), potassium hydroxide (1.12 g; 20 mmoles) and ethanol (25 ml) was refluxed for two hours. The reaction mixture was poured into ice cooled water and acidified with dilute hydrochloric acid to Congo Red. The precipitated solids were collected by filtration, washed and dried. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of solution of the title compound in a mixture of ethanol and water (85:15); m.p. 460 K; yield: 68%.

Refinement

H atoms bound to C were placed in geometric positions (C—H distance = 0.95 Å) using a riding model. H atoms on N and O had coordinates freely refined. Uiso values were set to 1.2Ueq (1.5Ueq for OH).

Figures

Fig. 1.
The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
Fig. 2.
Perspective view of the crystal packing showing hydrogen-bond interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

Crystal data

C10H9N3O2F000 = 424
Mr = 203.20Dx = 1.476 Mg m3
Monoclinic, P21/nMelting point: 460 K
Hall symbol: -P 2ynMo Kα radiation λ = 0.71073 Å
a = 3.7937 (5) ÅCell parameters from 2299 reflections
b = 21.613 (3) Åθ = 3.4–29.6º
c = 11.1580 (16) ŵ = 0.11 mm1
β = 92.170 (2)ºT = 150 (2) K
V = 914.2 (2) Å3Block, colourless
Z = 40.28 × 0.10 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer2800 independent reflections
Radiation source: fine-focus sealed tube1967 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 150(2) Kθmax = 30.6º
ω rotation with narrow frames scansθmin = 1.9º
Absorption correction: multi-scan(SADABS; Sheldrick, 2007)h = −5→5
Tmin = 0.971, Tmax = 0.993k = −30→30
10482 measured reflectionsl = −15→15

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: geom except NH & OH coords freely refined
R[F2 > 2σ(F2)] = 0.043H 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 reflectionsΔρmax = 0.34 e Å3
145 parametersΔρmin = −0.27 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
C10.0569 (4)0.34024 (6)−0.20989 (12)0.0196 (3)
H1−0.03450.3206−0.28070.023*
C20.0428 (4)0.40410 (7)−0.19887 (13)0.0242 (3)
H2−0.05480.4284−0.26280.029*
C30.1711 (4)0.43247 (7)−0.09461 (14)0.0262 (3)
H30.16230.4762−0.08730.031*
C40.3122 (4)0.39693 (7)−0.00110 (13)0.0235 (3)
H4C0.39580.41650.07070.028*
C50.3323 (4)0.33300 (6)−0.01161 (12)0.0196 (3)
H50.43130.30870.05220.024*
C60.2054 (3)0.30513 (6)−0.11682 (11)0.0168 (3)
N20.2312 (3)0.23989 (5)−0.13188 (9)0.0172 (2)
N30.3587 (3)0.21589 (5)−0.23810 (10)0.0205 (3)
C70.3374 (4)0.15556 (6)−0.22523 (12)0.0200 (3)
H70.40840.1268−0.28390.024*
C80.1976 (4)0.13829 (6)−0.11488 (11)0.0175 (3)
C90.1300 (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*
C100.1212 (4)0.07860 (6)−0.06630 (12)0.0198 (3)
O3−0.0099 (3)0.07239 (4)0.03332 (9)0.0247 (2)
O40.1962 (3)0.03107 (5)−0.13546 (9)0.0289 (3)
H40.132 (5)−0.0050 (10)−0.0983 (17)0.043*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0207 (7)0.0229 (7)0.0153 (6)0.0004 (5)0.0039 (5)0.0023 (5)
C20.0263 (7)0.0229 (7)0.0239 (7)0.0054 (6)0.0068 (6)0.0071 (5)
C30.0298 (8)0.0172 (6)0.0324 (8)−0.0002 (6)0.0113 (6)−0.0003 (5)
C40.0257 (7)0.0229 (7)0.0222 (7)−0.0043 (5)0.0052 (5)−0.0049 (5)
C50.0210 (7)0.0208 (6)0.0171 (6)−0.0009 (5)0.0011 (5)−0.0005 (5)
C60.0183 (6)0.0163 (6)0.0161 (6)−0.0002 (5)0.0046 (5)0.0009 (5)
N20.0238 (6)0.0162 (5)0.0119 (5)−0.0004 (4)0.0040 (4)0.0001 (4)
N30.0285 (6)0.0208 (6)0.0126 (5)0.0010 (5)0.0069 (4)−0.0007 (4)
C70.0266 (7)0.0192 (6)0.0144 (6)0.0006 (5)0.0042 (5)−0.0011 (5)
C80.0227 (6)0.0164 (6)0.0136 (6)−0.0001 (5)0.0029 (5)0.0000 (4)
C90.0195 (6)0.0164 (6)0.0133 (6)−0.0004 (5)0.0013 (5)0.0009 (4)
N40.0348 (7)0.0168 (5)0.0153 (5)−0.0022 (5)0.0095 (5)−0.0009 (4)
C100.0256 (7)0.0173 (6)0.0165 (6)−0.0001 (5)0.0034 (5)−0.0009 (5)
O30.0384 (6)0.0179 (5)0.0185 (5)−0.0016 (4)0.0096 (4)0.0006 (4)
O40.0493 (7)0.0158 (5)0.0228 (5)−0.0021 (5)0.0157 (5)−0.0022 (4)

Geometric parameters (Å, °)

C1—C21.387 (2)N2—N31.3968 (15)
C1—C61.3883 (18)N3—C71.3146 (18)
C1—H10.9500C7—C81.4092 (17)
C2—C31.387 (2)C7—H70.9500
C2—H20.9500C8—C91.4001 (17)
C3—C41.387 (2)C8—C101.4331 (18)
C3—H30.9500C9—N41.3438 (16)
C4—C51.3891 (19)N4—H4A0.903 (18)
C4—H4C0.9500N4—H4B0.876 (18)
C5—C61.3891 (18)C10—O31.2423 (16)
C5—H50.9500C10—O41.3221 (16)
C6—N21.4239 (16)O4—H40.92 (2)
N2—C91.3530 (16)
C2—C1—C6119.58 (13)C9—N2—C6128.69 (11)
C2—C1—H1120.2N3—N2—C6119.69 (10)
C6—C1—H1120.2C7—N3—N2104.53 (10)
C3—C2—C1120.06 (13)N3—C7—C8112.64 (12)
C3—C2—H2120.0N3—C7—H7123.7
C1—C2—H2120.0C8—C7—H7123.7
C4—C3—C2119.97 (13)C9—C8—C7104.64 (11)
C4—C3—H3120.0C9—C8—C10124.25 (12)
C2—C3—H3120.0C7—C8—C10131.08 (12)
C3—C4—C5120.55 (13)N4—C9—N2125.61 (12)
C3—C4—H4C119.7N4—C9—C8127.68 (12)
C5—C4—H4C119.7N2—C9—C8106.64 (11)
C4—C5—C6118.97 (13)C9—N4—H4A112.7 (11)
C4—C5—H5120.5C9—N4—H4B125.6 (11)
C6—C5—H5120.5H4A—N4—H4B120.0 (16)
C1—C6—C5120.86 (13)O3—C10—O4122.72 (12)
C1—C6—N2118.73 (12)O3—C10—C8121.96 (12)
C5—C6—N2120.40 (12)O4—C10—C8115.31 (12)
C9—N2—N3111.54 (10)C10—O4—H4109.2 (12)
C6—C1—C2—C3−1.1 (2)N3—C7—C8—C90.05 (16)
C1—C2—C3—C4−0.3 (2)N3—C7—C8—C10178.11 (14)
C2—C3—C4—C51.2 (2)N3—N2—C9—N4−176.22 (12)
C3—C4—C5—C6−0.7 (2)C6—N2—C9—N40.3 (2)
C2—C1—C6—C51.6 (2)N3—N2—C9—C80.98 (15)
C2—C1—C6—N2−177.34 (12)C6—N2—C9—C8177.55 (13)
C4—C5—C6—C1−0.7 (2)C7—C8—C9—N4176.51 (14)
C4—C5—C6—N2178.20 (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—C951.1 (2)C10—C8—C9—N2−178.85 (13)
C1—C6—N2—N346.33 (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—O4178.38 (13)
C6—N2—N3—C7−177.85 (12)C7—C8—C10—O40.7 (2)
N2—N3—C7—C80.51 (16)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N4—H4A···O30.903 (18)2.136 (18)2.8233 (16)132.3 (14)
N4—H4B···N3i0.876 (18)2.239 (18)3.0087 (17)146.5 (15)
O4—H4···O3ii0.92 (2)1.70 (2)2.6189 (14)178.4 (19)

Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x, −y, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2722).

References

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