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Acta Cryst. (2007). E63, o3764    [ doi:10.1107/S1600536807038809 ]

3-Phenyl-1H-pyrazole-5-carboxylic acid

X.-Y. Zhang, W. Liu, W. Tang and Y.-B. Lai

Abstract top

In the title compound, C10H8N2O2, the dihedral angle between the phenyl and pyrazole ring planes is 21.27 (6)°. Intermolecular O-H...O and N-H...N hydrogen bonds link the molecules into chains along c. These are further connected by intermolecular C-H...O hydrogen bonds, resulting in a two-dimensional framework.

Comment top

Pyrazole carboxylic acid and ester derivatives exhibit useful pharmaceutical properties, for example as agonists for the nicotinic acid receptor, refered to as RUP25 herein (Shin et al., 2005).

The molecular structure of (I) is shown in Fig. 1. The dihedral angle between the phenyl plane and the pyrazole plane is 21.27 (6) Å. The carboxylate C4—O1—O2 plane, is twisted slightly with respect to the pyrazole ring plane, the dihedral angle between them is 9.0 (1) °.

In the crystal structure, intermolecular O1—H1···O2i [symmetry code: (i) 1 − x, 2 − y, 1 − z] and N2—H2···N1ii [symmetry code: (ii) 1 − x, y − 1/2, −z + 3/2] hydrogen bonds link the molecules into chains, which are further connected by intermolecular C7—H7···O2iii [symmetry code: (iii) −x, y + 3/2, −z + 3/2] hydrogen bonds (C—O =3.531 (3) Å), resulting in a two-dimensional-dimensional framework.

Related literature top

For information on the pharmaceutical properties of the title compound, see: Shin et al. (2005).

Experimental top

To a stirred solution of NaOH (300 ml, 20%) at 350 K was added 5- phenyl-2H-pyrazole-3-carboxylic acid ethyl ester (21.6 g, 0.1 mol), and the solution was stirred for 8 h. The reaction mixture was cooled to 293 K, filtered. A white flocculent precipitate appeared when the filtrate was adjusted to pH = 3–5 using dilute HCl. The title compound (yield 16.90 g, 89.90%) was obtained by filtering this precipitate and crystals appropriate for data collection were obtained by recrystallization from acetone/methanol (1:1).

Refinement top

All H atoms bound to C were included in calculated positions and refined as riding with C—H= 0.93 Å, and Uiso(H)= 1.2 Ueq(C). Other hydrogen atoms were located in a difference Fourier map and refined freely with Uiso(H) = 1.5 Ueq(O) and Uiso(H) = 1.2 Ueq(N) respectively.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg & Berndt, 2005); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids.
[Figure 2] Fig. 2. The crystal packing of (I), view down the b axis, showing the one dimensional chain structure extending along the c axis. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. The crystal packing of (I), viewed down the b axis, showing the two-dimensional-dimensional hydrogen-bonded framework. Hydrogen bonds are shown as dashed lines.
3-Phenyl-1H-pyrazole-5-carboxylic acid top
Crystal data top
C10H8N2O2F(000) = 392
Mr = 188.18Dx = 1.350 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybcCell parameters from 1971 reflections
a = 10.2391 (12) Åθ = 2.7–25.0°
b = 5.3647 (6) ŵ = 0.10 mm−1
c = 17.5907 (17) ÅT = 291 K
β = 106.581 (8)°Block, colorless
V = 926.07 (17) Å30.32 × 0.30 × 0.18 mm
Z = 4
Data collection top
Rigaku Saturn
diffractometer		1817 independent reflections
Radiation source: rotating anode1377 reflections with I > 2σ(I)
confocalRint = 0.046
Detector resolution: 7.31 pixels mm-1θmax = 26.0°, θmin = 2.1°
ω scansh = −12→12
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		k = −6→6
Tmin = 0.970, Tmax = 0.983l = −21→21
9603 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.167H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.1024P)2]
where P = (Fo2 + 2Fc2)/3
1817 reflections(Δ/σ)max < 0.001
135 parametersΔρmax = 0.19 e Å−3
1 restraintΔρmin = −0.16 e Å−3
Crystal data top
C10H8N2O2V = 926.07 (17) Å3
Mr = 188.18Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.2391 (12) ŵ = 0.10 mm−1
b = 5.3647 (6) ÅT = 291 K
c = 17.5907 (17) Å0.32 × 0.30 × 0.18 mm
β = 106.581 (8)°
Data collection top
Rigaku Saturn
diffractometer		1817 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		1377 reflections with I > 2σ(I)
Tmin = 0.970, Tmax = 0.983Rint = 0.046
9603 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.167Δρmax = 0.19 e Å−3
S = 1.07Δρmin = −0.16 e Å−3
1817 reflectionsAbsolute structure: ?
135 parametersFlack parameter: ?
1 restraintRogers parameter: ?
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
xyzUiso*/Ueq
O10.54576 (15)0.8690 (3)0.59886 (8)0.0705 (5)
H10.571 (2)0.983 (4)0.5702 (13)0.106*
O20.38316 (15)0.7806 (3)0.48748 (7)0.0705 (5)
N10.45958 (15)0.4857 (3)0.67529 (8)0.0535 (5)
N20.38121 (16)0.3093 (3)0.69483 (9)0.0529 (5)
H20.4141 (19)0.226 (4)0.7415 (12)0.063*
C10.39024 (17)0.5507 (3)0.60188 (9)0.0486 (5)
C20.26909 (17)0.4153 (3)0.57510 (10)0.0510 (5)
H2A0.20450.42750.52590.061*
C30.26539 (18)0.2603 (3)0.63673 (10)0.0476 (5)
C40.44173 (19)0.7448 (3)0.55878 (11)0.0526 (5)
C50.16279 (18)0.0802 (3)0.64533 (10)0.0494 (5)
C60.0304 (2)0.0999 (4)0.59687 (12)0.0617 (6)
H60.00710.22800.55990.074*
C7−0.0674 (2)−0.0702 (5)0.60325 (14)0.0744 (7)
H7−0.1560−0.05520.57040.089*
C8−0.0356 (3)−0.2601 (4)0.65715 (15)0.0775 (7)
H8−0.1018−0.37470.66070.093*
C90.0940 (3)−0.2798 (4)0.70570 (14)0.0748 (7)
H90.1157−0.40830.74270.090*
C100.1939 (2)−0.1121 (3)0.70098 (12)0.0606 (6)
H100.2818−0.12750.73490.073*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0759 (10)0.0725 (10)0.0537 (9)−0.0270 (7)0.0033 (7)0.0068 (7)
O20.0755 (10)0.0812 (10)0.0451 (8)−0.0211 (8)0.0018 (7)0.0123 (7)
N10.0577 (9)0.0554 (9)0.0418 (9)−0.0068 (7)0.0053 (7)0.0030 (7)
N20.0602 (10)0.0535 (9)0.0394 (9)−0.0042 (7)0.0053 (7)0.0062 (7)
C10.0568 (11)0.0479 (10)0.0386 (9)−0.0023 (8)0.0096 (8)0.0000 (7)
C20.0549 (11)0.0528 (10)0.0381 (10)−0.0035 (8)0.0016 (8)0.0014 (7)
C30.0552 (11)0.0441 (10)0.0402 (9)0.0009 (7)0.0083 (8)0.0003 (7)
C40.0560 (11)0.0533 (11)0.0448 (11)−0.0049 (8)0.0083 (9)−0.0010 (8)
C50.0588 (11)0.0454 (10)0.0461 (10)−0.0029 (8)0.0181 (9)−0.0055 (8)
C60.0646 (12)0.0622 (12)0.0561 (12)−0.0084 (9)0.0136 (10)−0.0043 (9)
C70.0669 (14)0.0816 (16)0.0772 (16)−0.0174 (11)0.0244 (11)−0.0203 (12)
C80.0873 (17)0.0698 (15)0.0907 (18)−0.0229 (13)0.0502 (15)−0.0199 (13)
C90.106 (2)0.0524 (12)0.0796 (16)−0.0020 (12)0.0487 (16)0.0045 (11)
C100.0739 (13)0.0519 (11)0.0594 (13)0.0036 (9)0.0246 (10)0.0050 (9)
Geometric parameters (Å, °) top
O1—C41.283 (2)C5—C61.384 (3)
O1—H10.876 (10)C5—C101.395 (3)
O2—C41.241 (2)C6—C71.383 (3)
N1—C11.330 (2)C6—H60.9300
N1—N21.347 (2)C7—C81.366 (3)
N2—C31.352 (2)C7—H70.9300
N2—H20.91 (2)C8—C91.362 (3)
C1—C21.398 (2)C8—H80.9300
C1—C41.472 (3)C9—C101.382 (3)
C2—C31.375 (2)C9—H90.9300
C2—H2A0.9300C10—H100.9300
C3—C51.467 (2)
C4—O1—H1112.4 (16)C6—C5—C3119.40 (16)
C1—N1—N2103.88 (14)C10—C5—C3122.18 (17)
N1—N2—C3113.67 (14)C7—C6—C5120.3 (2)
N1—N2—H2118.8 (12)C7—C6—H6119.9
C3—N2—H2127.2 (13)C5—C6—H6119.9
N1—C1—C2111.56 (16)C8—C7—C6120.9 (2)
N1—C1—C4121.00 (16)C8—C7—H7119.5
C2—C1—C4127.44 (15)C6—C7—H7119.5
C3—C2—C1105.65 (15)C9—C8—C7119.3 (2)
C3—C2—H2A127.2C9—C8—H8120.4
C1—C2—H2A127.2C7—C8—H8120.4
N2—C3—C2105.24 (15)C8—C9—C10121.2 (2)
N2—C3—C5123.34 (15)C8—C9—H9119.4
C2—C3—C5131.40 (17)C10—C9—H9119.4
O2—C4—O1124.12 (18)C9—C10—C5119.9 (2)
O2—C4—C1119.29 (16)C9—C10—H10120.0
O1—C4—C1116.59 (16)C5—C10—H10120.0
C6—C5—C10118.42 (17)
C1—N1—N2—C30.0 (2)N2—C3—C5—C6157.93 (18)
N2—N1—C1—C2−0.3 (2)C2—C3—C5—C6−20.1 (3)
N2—N1—C1—C4179.23 (16)N2—C3—C5—C10−22.1 (3)
N1—C1—C2—C30.4 (2)C2—C3—C5—C10159.78 (19)
C4—C1—C2—C3−179.07 (18)C10—C5—C6—C7−0.9 (3)
N1—N2—C3—C20.2 (2)C3—C5—C6—C7179.05 (18)
N1—N2—C3—C5−178.32 (16)C5—C6—C7—C80.0 (3)
C1—C2—C3—N2−0.33 (19)C6—C7—C8—C90.7 (3)
C1—C2—C3—C5178.01 (17)C7—C8—C9—C10−0.4 (3)
N1—C1—C4—O2171.64 (19)C8—C9—C10—C5−0.5 (3)
C2—C1—C4—O2−9.0 (3)C6—C5—C10—C91.1 (3)
N1—C1—C4—O1−8.9 (3)C3—C5—C10—C9−178.80 (18)
C2—C1—C4—O1170.48 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N1i0.91 (2)2.10 (2)2.961 (2)158.0 (17)
O1—H1···O2ii0.88 (1)1.77 (1)2.6462 (19)178 (2)
C7—H7···O2iii0.932.703.5311 (25)150
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N1i0.91 (2)2.10 (2)2.961 (2)158.0 (17)
O1—H1···O2ii0.88 (1)1.77 (1)2.6462 (19)178 (2)
C7—H7···O2iii0.932.703.5311 (25)150
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, −y+2, −z+1; (iii) −x, −y+1, −z+1.
references
References top

Brandenburg, K. & Berndt, M. (2005). DIAMOND. Release 3.0c. Crystal Impact GbR, Bonn, Germany.

Rigaku/MSC (2005). CrystalClear and CrystalStructure. Versions 3.70. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Shin, Y. J., Semple, G., Gharbaoui, T., Decaire, M., Skinner, P. J. & Averbuj, C. (2005). Canadian Patent No. CAP2528834.