Methyl 5-phenyl-1H-pyrazole-3-car­boxyl­ate

Zhou, G.; An, Y.; Han, J.; Ge, M.; Xing, Y.

doi:10.1107/S1600536807052452

Methyl 5-phenyl-1H-pyrazole-3-carboxylate

G. Zhou, Y. An, J. Han, M. Ge and Y. Xing

The title compound, C₁₁H₁₀N₂O₂, was prepared by the esterfication of 5-phenyl-1H-pyrazole-3-carboxylic acid with methanol. The phenyl ring is rotated out of the pyrazole plane, forming a dihedral angle of 6.4 (1)°. The crystal structure is stabilized by intermolecular aromatic π–π interactions [with a centroid–centroid distance of 3.862 (3) Å between the pyrazole ring and the benzene ring of a neighboring molecule], and by three different types of hydrogen bond (N—H

N, N—H

O and C—H

O).

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052452/lx2019sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052452/lx2019Isup2.hkl Contains datablock I

CCDC reference: 630270

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Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.044
wR factor = 0.120
Data-to-parameter ratio = 16.1

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No syntax errors found



Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   0 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
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Comment top

The coordination chemistry of pyrazole and its derivatives has been received great attention since poly(pyrazolyl)borate was found (Trofimenko, 1972). The electron donor (nitrogen) of non-substituted pyrazole unit can coordinate to many metal ions such as copper and vanadium, etc. (Otieno et al., 2002; Xing et al., 2007). When the carboxyl group as the substitutent at three or five position on the pyrazole ring is present, this will enhance the coordination capability of the pyrazole ring, and the substituted carboxyl group and the pyrazole ring with the metal ion can form a steady five-member cycle (Roussel et al., 2006). Herein we report the molecular and crystal structure of the title compound, methyl 5-phenyl-1H-pyrazole-3-carboxylic acid (Fig. 1).

The crystal structure of the title compound (Fig. 1) indicates that the phenyl plane was not coplanar with the pyrazole plane, with their dihedron angle of 6.4 (1)°. All the bond lengths of the pyrazole ring are close to the corresponding bond lengths of ethyl 5-phenyl-1H-pyrazole-3-carboxylate as reported previously (Infantes et al., 1999). The molecular packing (Fig. 2) is stabilized by π···π stacking interactions between the pyrazole ring and the benzene ring of adjacent molecule, with the Cg1···Cg2 distance of 3.862 (3) Å (Cg1 and Cg2 are the centorids of the C7—C9/N2—N1 pyrazole ring and the C1—C6 benzene ring, respectively; symmetry code as in Fig. 2). The molecular packing is further stabilized by three different hydrogen bonds (Fig. 2 and Table 1).

Related literature top

For the coordination chemistry of similar pyrazol derivatives, see: Trofimenko (1972); Xing et al. (2007); Infantes et al. (1999). For related literature, see: Otieno et al. (2002); Roussel et al. (2006).

Experimental top

CuCl₂ (40.0 mg, 0.21 mmol) was added into the methanol (10 ml) gently, the suspension was kept stirring at room temperature until the solution turned clear green, after which, 5-phenyl-1H-pyrazole-3-carboxylic acid (36.3 mg, 0.21 mmol) was added, then HCl (6.0M, 1.0 ml) was dropped in and stirred for 7 h continuously. Precipitate was filtered off and the filtrate was kept in conical flask for about one month and some pretty colorless rhombic crystals were obtained from the solution, dried in vacuum. Yield: 31.2%. Crystal of the title compound suitable for single-crystal X-ray diffraction was selected directly from the sample as prepared.

Structure description top

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: SHELXTL (Sheldrick, 1997a); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997b); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL (Sheldrick, 1997a) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 1997a).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoides drawn at the 50% probability level.
	Fig. 2. Packing arrangement of the title compound along b axis. Cg denotes the ring centroids. [Symmetry code: (i) -x + 1/2, y - 1/2, -z + 1/2; (ii) -x, -y + 1,-z; (iii) -x + 1/2, y + 1/2, -z + 1/2; (iv) x, y - 1, z; (v) x, y + 1, z.]

Methyl 5-phenyl-1H-pyrazole-3-carboxylate top

Crystal data top

C₁₁H₁₀N₂O₂	F(000) = 848
M_r = 202.21	D_x = 1.331 Mg m⁻³
Monoclinic, C2/c	Melting point = 185.5–185.9 K
Hall symbol: -c 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 24.540 (6) Å	Cell parameters from 2416 reflections
b = 5.980 (1) Å	θ = 2.5–29.0°
c = 16.387 (4) Å	µ = 0.09 mm⁻¹
β = 122.933 (2)°	T = 293 K
V = 2018.3 (8) Å³	Rhombic, colorless
Z = 8	0.20 × 0.15 × 0.05 mm

Data collection top

Bruker P4 diffractometer	1612 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 27.0°, θ_min = 2.5°
Detector resolution: 10.0 pixels mm^-1	h = −31→31
ω scans	k = −7→5
5591 measured reflections	l = −20→20
2185 independent 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0548P)² + 0.752P] where P = (F_o² + 2F_c²)/3
2185 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₁H₁₀N₂O₂	V = 2018.3 (8) Å³
M_r = 202.21	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 24.540 (6) Å	µ = 0.09 mm⁻¹
b = 5.980 (1) Å	T = 293 K
c = 16.387 (4) Å	0.20 × 0.15 × 0.05 mm
β = 122.933 (2)°

Data collection top

Bruker P4 diffractometer	1612 reflections with I > 2σ(I)
5591 measured reflections	R_int = 0.022
2185 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.05	Δρ_max = 0.21 e Å⁻³
2185 reflections	Δρ_min = −0.22 e Å⁻³
136 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.17604 (8)	−0.1789 (3)	0.03661 (12)	0.0476 (4)
H1	0.2185	−0.1488	0.0870	0.057*
C2	0.16326 (10)	−0.3570 (3)	−0.02517 (13)	0.0580 (5)
H2	0.1973	−0.4456	−0.0162	0.070*
C3	0.10077 (10)	−0.4042 (3)	−0.09971 (14)	0.0594 (5)
H3	0.0924	−0.5242	−0.1410	0.071*
C4	0.05089 (9)	−0.2733 (3)	−0.11276 (13)	0.0563 (5)
H4	0.0085	−0.3054	−0.1631	0.068*
C5	0.06269 (8)	−0.0947 (3)	−0.05225 (11)	0.0471 (4)
H5	0.0283	−0.0069	−0.0623	0.057*
C6	0.12571 (7)	−0.0444 (3)	0.02380 (10)	0.0365 (4)
C7	0.13661 (7)	0.1465 (3)	0.08722 (10)	0.0349 (3)
C8	0.09485 (7)	0.3081 (3)	0.08165 (10)	0.0373 (4)
H8	0.0508	0.3221	0.0345	0.045*
C9	0.13253 (7)	0.4464 (3)	0.16157 (10)	0.0358 (4)
C10	0.11091 (8)	0.6429 (3)	0.19061 (11)	0.0398 (4)
C11	0.14358 (11)	0.9382 (3)	0.30373 (15)	0.0663 (6)
H11A	0.1821	0.9962	0.3604	0.099*
H11B	0.1126	0.8983	0.3198	0.099*
H11C	0.1252	1.0502	0.2537	0.099*
N1	0.19519 (6)	0.1955 (2)	0.16806 (9)	0.0405 (3)
H1N	0.2296	0.1177	0.1872	0.049*
N2	0.19433 (6)	0.3774 (2)	0.21536 (9)	0.0413 (3)
O1	0.05575 (6)	0.7053 (2)	0.14871 (10)	0.0640 (4)
O2	0.15988 (6)	0.7429 (2)	0.26949 (8)	0.0522 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0431 (9)	0.0528 (11)	0.0442 (9)	0.0067 (8)	0.0219 (8)	−0.0001 (8)
C2	0.0669 (13)	0.0531 (11)	0.0609 (11)	0.0143 (9)	0.0392 (10)	0.0002 (9)
C3	0.0805 (14)	0.0510 (11)	0.0535 (11)	−0.0026 (10)	0.0409 (11)	−0.0100 (9)
C4	0.0554 (11)	0.0605 (12)	0.0454 (9)	−0.0107 (9)	0.0225 (8)	−0.0135 (9)
C5	0.0383 (9)	0.0530 (10)	0.0430 (9)	−0.0004 (8)	0.0176 (7)	−0.0066 (8)
C6	0.0374 (8)	0.0391 (8)	0.0326 (7)	0.0008 (6)	0.0188 (7)	0.0036 (6)
C7	0.0292 (7)	0.0378 (8)	0.0328 (7)	−0.0017 (6)	0.0138 (6)	0.0023 (6)
C8	0.0254 (7)	0.0401 (9)	0.0361 (8)	0.0004 (6)	0.0100 (6)	0.0011 (6)
C9	0.0296 (8)	0.0363 (8)	0.0371 (8)	−0.0011 (6)	0.0152 (6)	0.0030 (6)
C10	0.0383 (9)	0.0364 (9)	0.0426 (8)	−0.0022 (7)	0.0207 (7)	0.0010 (7)
C11	0.0917 (16)	0.0487 (12)	0.0713 (13)	−0.0093 (10)	0.0526 (12)	−0.0182 (10)
N1	0.0269 (7)	0.0431 (8)	0.0414 (7)	0.0048 (5)	0.0121 (6)	−0.0022 (6)
N2	0.0322 (7)	0.0402 (7)	0.0412 (7)	0.0002 (6)	0.0132 (6)	−0.0041 (6)
O1	0.0428 (7)	0.0590 (8)	0.0755 (9)	0.0109 (6)	0.0227 (7)	−0.0104 (7)
O2	0.0491 (7)	0.0479 (7)	0.0538 (7)	−0.0055 (5)	0.0242 (6)	−0.0153 (6)

Geometric parameters (Å, º) top

C1—C2	1.383 (2)	C7—C8	1.375 (2)
C1—C6	1.391 (2)	C8—C9	1.392 (2)
C1—H1	0.9300	C8—H8	0.9300
C2—C3	1.374 (3)	C9—N2	1.339 (2)
C2—H2	0.9300	C9—C10	1.471 (2)
C3—C4	1.368 (3)	C10—O1	1.197 (2)
C3—H3	0.9300	C10—O2	1.336 (2)
C4—C5	1.377 (2)	C11—O2	1.443 (2)
C4—H4	0.9300	C11—H11A	0.9600
C5—C6	1.393 (2)	C11—H11B	0.9600
C5—H5	0.9300	C11—H11C	0.9600
C6—C7	1.467 (2)	N1—N2	1.342 (2)
C7—N1	1.355 (2)	N1—H1N	0.8600

C2—C1—C6	120.36 (16)	C7—C8—C9	105.38 (13)
C2—C1—H1	119.8	C7—C8—H8	127.3
C6—C1—H1	119.8	C9—C8—H8	127.3
C3—C2—C1	120.56 (17)	N2—C9—C8	111.80 (13)
C3—C2—H2	119.7	N2—C9—C10	120.80 (13)
C1—C2—H2	119.7	C8—C9—C10	127.38 (14)
C4—C3—C2	119.54 (17)	O1—C10—O2	123.87 (15)
C4—C3—H3	120.2	O1—C10—C9	123.93 (14)
C2—C3—H3	120.2	O2—C10—C9	112.21 (13)
C3—C4—C5	120.74 (17)	O2—C11—H11A	109.5
C3—C4—H4	119.6	O2—C11—H11B	109.5
C5—C4—H4	119.6	H11A—C11—H11B	109.5
C4—C5—C6	120.56 (16)	O2—C11—H11C	109.5
C4—C5—H5	119.7	H11A—C11—H11C	109.5
C6—C5—H5	119.7	H11B—C11—H11C	109.5
C1—C6—C5	118.25 (15)	N2—N1—C7	113.48 (12)
C1—C6—C7	122.54 (14)	N2—N1—H1N	123.3
C5—C6—C7	119.21 (14)	C7—N1—H1N	123.3
N1—C7—C8	105.59 (13)	C9—N2—N1	103.74 (12)
N1—C7—C6	123.29 (13)	C10—O2—C11	116.42 (14)
C8—C7—C6	131.11 (13)

C6—C1—C2—C3	−0.3 (3)	C7—C8—C9—N2	−0.41 (18)
C1—C2—C3—C4	0.1 (3)	C7—C8—C9—C10	−178.60 (15)
C2—C3—C4—C5	0.2 (3)	N2—C9—C10—O1	−175.69 (16)
C3—C4—C5—C6	−0.3 (3)	C8—C9—C10—O1	2.4 (3)
C2—C1—C6—C5	0.2 (2)	N2—C9—C10—O2	4.0 (2)
C2—C1—C6—C7	−179.99 (15)	C8—C9—C10—O2	−178.00 (14)
C4—C5—C6—C1	0.1 (2)	C8—C7—N1—N2	0.08 (17)
C4—C5—C6—C7	−179.73 (15)	C6—C7—N1—N2	179.93 (13)
C1—C6—C7—N1	−6.1 (2)	C8—C9—N2—N1	0.45 (17)
C5—C6—C7—N1	173.74 (14)	C10—C9—N2—N1	178.78 (13)
C1—C6—C7—C8	173.71 (16)	C7—N1—N2—C9	−0.33 (17)
C5—C6—C7—C8	−6.5 (2)	O1—C10—O2—C11	−0.4 (2)
N1—C7—C8—C9	0.19 (16)	C9—C10—O2—C11	179.90 (14)
C6—C7—C8—C9	−179.64 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2ⁱ	0.86	2.20	2.998 (2)	153
N1—H1N···O2ⁱ	0.86	2.52	3.134 (2)	130
C5—H5···O1ⁱⁱ	0.93	2.52	3.372 (2)	153

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₂O₂
M_r	202.21
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	24.540 (6), 5.980 (1), 16.387 (4)
β (°)	122.933 (2)
V (Å³)	2018.3 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.15 × 0.05

Data collection
Diffractometer	Bruker P4
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5591, 2185, 1612
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.120, 1.05
No. of reflections	2185
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.22

Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 1997b), SHELXL97 (Sheldrick, 1997b), SHELXTL (Sheldrick, 1997a) and DIAMOND (Brandenburg, 1998).