Ethyl 1-benzyl-3-(4-fluoro­phen­yl)-1H-pyrazole-5-carboxyl­ate

Han, Z.; Zheng, H.-L.; Tian, X.-L.

doi:10.1107/S1600536811002340

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o511

doi:10.1107/S1600536811002340

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Ethyl 1-benzyl-3-(4-fluorophenyl)-1H-pyrazole-5-carboxylate

Zhe Han,^a Hong-Liang Zheng ^a and Xue-Lei Tian ^a ^*

^aKey Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (Ministry of Education), Shandong University, Jinan 250061, People's Republic of China
^*Correspondence e-mail: tianxuelei@sdu.edu.cn

(Received 10 January 2011; accepted 16 January 2011; online 29 January 2011)

In the title compound, C₁₉H₁₇FN₂O₂, the pyrazole ring makes dihedral angles of 4.57 (16) and 81.19 (18)° with the fluorophenyl and benzene rings, respectively.

Related literature

For the applications of nitrogen-containing heterocyclic compounds in agrochemical and pharmaceutical fields, see: Ge et al. (2009a ,b ). For related structures, see: Ge et al. (2007a ,b ).

Experimental

Crystal data

C₁₉H₁₇FN₂O₂
M_r = 324.35
Triclinic, $[P \overline 1]$
a = 8.119 (8) Å
b = 10.173 (6) Å
c = 10.814 (6) Å
α = 108.672 (15)°
β = 102.567 (16)°
γ = 91.460 (16)°
V = 821.5 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.21 × 0.16 × 0.12 mm

Data collection

Bruker SMART CD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.981, T_max = 0.989
4034 measured reflections
2844 independent reflections
2014 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.084
wR(F²) = 0.245
S = 1.07
2844 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811002340/jh2256sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002340/jh2256Isup2.hkl

checkCIF report

Comment top

Synthesis of nitrogen-containing heterocyclic compounds has been a subject of great interest due to the wide application in agrochemical and pharmaceutical fields (Ge et al.; 2007a, 2007b, 2009a, 2009b). Some pyrazole derivatives which belong to this category have been of interest for their biological activities. We report here the crystal structure of the title compound, (I) (Fig. 1)

Related literature top

For the applications of nitrogen-containing heterocyclic compounds in agrochemical and pharmaceutical fields, see: Ge et al. (2009a,b). For related structures, see: Ge et al.(2007a,b). AUTHOR: please remember to subdivide this section in future

Experimental top

A mixture of ethyl 3-(4-fluorophenyl)-1H-pyrazole-5-carboxylate (0.02 mol), benzyl chloride (0.0024 mol) and potassium carbonate (0.02 mol) in acetonitrile (100 ml) was heated to reflux for 10 h. The solvent was removed under reduced pressure and an product was isolated by column chromatography on silica gel (yield 76%). Crystals of (I) suitable for X-ray diffraction were obtained by slow cooling of the refluxed solution of the product in ethyl acetate at room temperature for 2 d.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing displacement ellipsoids drawn at the 50% probability level.

Ethyl 1-benzyl-3-(4-fluorophenyl)-1H-pyrazole-5-carboxylate top

Crystal data top

C₁₉H₁₇FN₂O₂	Z = 2
M_r = 324.35	F(000) = 340
Triclinic, P1	D_x = 1.311 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.119 (8) Å	Cell parameters from 1645 reflections
b = 10.173 (6) Å	θ = 2.4–27.3°
c = 10.814 (6) Å	µ = 0.09 mm⁻¹
α = 108.672 (15)°	T = 298 K
β = 102.567 (16)°	Block, white
γ = 91.460 (16)°	0.21 × 0.16 × 0.12 mm
V = 821.5 (10) Å³

Data collection top

Bruker SMART CD area-detector diffractometer	2844 independent reflections
Radiation source: fine-focus sealed tube	2014 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
phi and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→6
T_min = 0.981, T_max = 0.989	k = −12→11
4034 measured reflections	l = −12→12

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)] = 0.084	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.245	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.165P)²] where P = (F_o² + 2F_c²)/3
2844 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₉H₁₇FN₂O₂	γ = 91.460 (16)°
M_r = 324.35	V = 821.5 (10) Å³
Triclinic, P1	Z = 2
a = 8.119 (8) Å	Mo Kα radiation
b = 10.173 (6) Å	µ = 0.09 mm⁻¹
c = 10.814 (6) Å	T = 298 K
α = 108.672 (15)°	0.21 × 0.16 × 0.12 mm
β = 102.567 (16)°

Data collection top

Bruker SMART CD area-detector diffractometer	2844 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2014 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.989	R_int = 0.030
4034 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.084	0 restraints
wR(F²) = 0.245	H-atom parameters constrained
S = 1.07	Δρ_max = 0.51 e Å⁻³
2844 reflections	Δρ_min = −0.30 e Å⁻³
217 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
F1	0.0446 (3)	0.7940 (3)	1.0242 (2)	0.0941 (8)
O1	0.3457 (3)	0.4182 (3)	0.1271 (2)	0.0856 (8)
O2	0.3605 (2)	0.2792 (2)	0.2513 (2)	0.0633 (6)
N1	0.2763 (3)	0.6363 (2)	0.3527 (2)	0.0524 (6)
N2	0.2347 (3)	0.7094 (3)	0.4667 (2)	0.0544 (6)
C1	0.0891 (4)	0.7506 (4)	0.9042 (3)	0.0659 (9)
C2	0.1320 (4)	0.6187 (4)	0.8574 (3)	0.0681 (9)
H2	0.1317	0.5585	0.9063	0.082*
C3	0.1762 (4)	0.5763 (3)	0.7355 (3)	0.0604 (8)
H3	0.2066	0.4865	0.7023	0.072*
C4	0.1760 (3)	0.6651 (3)	0.6618 (3)	0.0486 (7)
C5	0.1315 (4)	0.7985 (3)	0.7127 (3)	0.0620 (8)
H5	0.1308	0.8594	0.6642	0.074*
C6	0.0878 (4)	0.8422 (4)	0.8360 (3)	0.0694 (9)
H6	0.0584	0.9321	0.8710	0.083*
C7	0.2232 (3)	0.6190 (3)	0.5320 (3)	0.0476 (7)
C8	0.2607 (3)	0.4883 (3)	0.4600 (3)	0.0507 (7)
H8	0.2623	0.4084	0.4842	0.061*
C9	0.2947 (3)	0.5017 (3)	0.3453 (3)	0.0496 (7)
C10	0.3367 (3)	0.3994 (3)	0.2303 (3)	0.0560 (8)
C11	0.3982 (4)	0.1676 (3)	0.1414 (3)	0.0707 (9)
H11A	0.5020	0.1943	0.1210	0.085*
H11B	0.3066	0.1471	0.0614	0.085*
C12	0.4175 (5)	0.0438 (4)	0.1851 (4)	0.0898 (12)
H12A	0.5120	0.0638	0.2615	0.135*
H12B	0.4370	−0.0338	0.1131	0.135*
H12C	0.3160	0.0211	0.2091	0.135*
C13	0.3159 (3)	0.7111 (3)	0.2662 (3)	0.0595 (8)
H13A	0.2573	0.7947	0.2804	0.071*
H13B	0.2741	0.6528	0.1730	0.071*
C14	0.5029 (3)	0.7517 (3)	0.2919 (3)	0.0532 (7)
C15	0.5833 (4)	0.7185 (3)	0.1874 (3)	0.0629 (8)
H15	0.5221	0.6684	0.1006	0.075*
C16	0.7528 (5)	0.7588 (4)	0.2109 (5)	0.0802 (11)
H16	0.8057	0.7374	0.1397	0.096*
C17	0.8439 (4)	0.8301 (4)	0.3378 (5)	0.0899 (13)
H17	0.9591	0.8567	0.3533	0.108*
C18	0.7659 (5)	0.8628 (4)	0.4434 (5)	0.0916 (12)
H18	0.8287	0.9107	0.5302	0.110*
C19	0.5959 (4)	0.8248 (4)	0.4209 (3)	0.0698 (9)
H19	0.5431	0.8480	0.4921	0.084*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0974 (14)	0.131 (2)	0.0598 (13)	0.0193 (13)	0.0397 (11)	0.0254 (13)
O1	0.126 (2)	0.0790 (17)	0.0587 (15)	0.0083 (14)	0.0397 (14)	0.0212 (13)
O2	0.0740 (13)	0.0592 (13)	0.0566 (13)	0.0104 (10)	0.0235 (10)	0.0135 (11)
N1	0.0546 (12)	0.0581 (15)	0.0503 (14)	0.0089 (10)	0.0189 (10)	0.0215 (12)
N2	0.0537 (12)	0.0584 (15)	0.0572 (15)	0.0104 (10)	0.0201 (11)	0.0225 (13)
C1	0.0529 (16)	0.092 (2)	0.0498 (18)	0.0047 (15)	0.0175 (13)	0.0157 (18)
C2	0.0730 (19)	0.081 (2)	0.055 (2)	0.0028 (16)	0.0184 (16)	0.0284 (18)
C3	0.0653 (17)	0.0633 (19)	0.0573 (18)	0.0065 (14)	0.0194 (14)	0.0233 (16)
C4	0.0415 (13)	0.0544 (16)	0.0481 (16)	0.0016 (11)	0.0106 (11)	0.0149 (14)
C5	0.0641 (17)	0.066 (2)	0.060 (2)	0.0139 (14)	0.0200 (14)	0.0230 (17)
C6	0.0698 (18)	0.074 (2)	0.064 (2)	0.0205 (16)	0.0261 (16)	0.0144 (19)
C7	0.0412 (12)	0.0525 (16)	0.0491 (16)	0.0030 (11)	0.0098 (11)	0.0178 (14)
C8	0.0479 (13)	0.0551 (18)	0.0507 (17)	0.0010 (11)	0.0126 (12)	0.0195 (14)
C9	0.0434 (13)	0.0542 (17)	0.0481 (16)	0.0010 (11)	0.0101 (11)	0.0137 (13)
C10	0.0517 (15)	0.0607 (19)	0.0514 (18)	−0.0028 (12)	0.0121 (13)	0.0137 (15)
C11	0.083 (2)	0.066 (2)	0.058 (2)	0.0123 (16)	0.0230 (16)	0.0080 (18)
C12	0.117 (3)	0.065 (2)	0.087 (3)	0.018 (2)	0.033 (2)	0.019 (2)
C13	0.0616 (16)	0.070 (2)	0.0578 (18)	0.0117 (14)	0.0170 (14)	0.0345 (16)
C14	0.0622 (15)	0.0529 (17)	0.0557 (18)	0.0109 (12)	0.0219 (13)	0.0278 (15)
C15	0.0761 (19)	0.0630 (19)	0.061 (2)	0.0124 (14)	0.0303 (16)	0.0270 (16)
C16	0.080 (2)	0.081 (2)	0.103 (3)	0.0177 (19)	0.048 (2)	0.045 (2)
C17	0.060 (2)	0.086 (3)	0.139 (4)	0.0027 (18)	0.028 (2)	0.057 (3)
C18	0.081 (2)	0.088 (3)	0.095 (3)	−0.0153 (19)	0.005 (2)	0.029 (2)
C19	0.078 (2)	0.073 (2)	0.056 (2)	−0.0005 (16)	0.0187 (16)	0.0186 (17)

Geometric parameters (Å, º) top

F1—C1	1.362 (4)	C9—C10	1.456 (4)
O1—C10	1.208 (4)	C11—C12	1.480 (5)
O2—C10	1.325 (4)	C11—H11A	0.9700
O2—C11	1.451 (4)	C11—H11B	0.9700
N1—N2	1.340 (3)	C12—H12A	0.9600
N1—C9	1.360 (4)	C12—H12B	0.9600
N1—C13	1.460 (3)	C12—H12C	0.9600
N2—C7	1.339 (3)	C13—C14	1.504 (4)
C1—C2	1.358 (5)	C13—H13A	0.9700
C1—C6	1.360 (5)	C13—H13B	0.9700
C2—C3	1.379 (4)	C14—C15	1.380 (4)
C2—H2	0.9300	C14—C19	1.385 (4)
C3—C4	1.382 (4)	C15—C16	1.371 (5)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.382 (4)	C16—C17	1.360 (6)
C4—C7	1.470 (4)	C16—H16	0.9300
C5—C6	1.392 (4)	C17—C18	1.378 (6)
C5—H5	0.9300	C17—H17	0.9300
C6—H6	0.9300	C18—C19	1.372 (5)
C7—C8	1.388 (4)	C18—H18	0.9300
C8—C9	1.374 (4)	C19—H19	0.9300
C8—H8	0.9300

C10—O2—C11	116.1 (3)	O2—C11—H11A	110.3
N2—N1—C9	111.5 (2)	C12—C11—H11A	110.3
N2—N1—C13	118.3 (2)	O2—C11—H11B	110.3
C9—N1—C13	129.6 (2)	C12—C11—H11B	110.3
C7—N2—N1	105.6 (2)	H11A—C11—H11B	108.5
C2—C1—C6	122.8 (3)	C11—C12—H12A	109.5
C2—C1—F1	119.1 (3)	C11—C12—H12B	109.5
C6—C1—F1	118.1 (3)	H12A—C12—H12B	109.5
C1—C2—C3	118.4 (3)	C11—C12—H12C	109.5
C1—C2—H2	120.8	H12A—C12—H12C	109.5
C3—C2—H2	120.8	H12B—C12—H12C	109.5
C2—C3—C4	121.1 (3)	N1—C13—C14	112.9 (2)
C2—C3—H3	119.5	N1—C13—H13A	109.0
C4—C3—H3	119.5	C14—C13—H13A	109.0
C5—C4—C3	118.9 (3)	N1—C13—H13B	109.0
C5—C4—C7	120.4 (3)	C14—C13—H13B	109.0
C3—C4—C7	120.7 (3)	H13A—C13—H13B	107.8
C4—C5—C6	120.3 (3)	C15—C14—C19	119.2 (3)
C4—C5—H5	119.8	C15—C14—C13	120.6 (3)
C6—C5—H5	119.8	C19—C14—C13	120.1 (3)
C1—C6—C5	118.5 (3)	C16—C15—C14	120.3 (3)
C1—C6—H6	120.7	C16—C15—H15	119.8
C5—C6—H6	120.7	C14—C15—H15	119.8
N2—C7—C8	110.7 (2)	C17—C16—C15	120.3 (3)
N2—C7—C4	119.9 (2)	C17—C16—H16	119.9
C8—C7—C4	129.3 (3)	C15—C16—H16	119.9
C9—C8—C7	105.6 (3)	C16—C17—C18	120.1 (3)
C9—C8—H8	127.2	C16—C17—H17	120.0
C7—C8—H8	127.2	C18—C17—H17	120.0
N1—C9—C8	106.6 (2)	C19—C18—C17	120.2 (4)
N1—C9—C10	122.5 (3)	C19—C18—H18	119.9
C8—C9—C10	130.9 (3)	C17—C18—H18	119.9
O1—C10—O2	123.3 (3)	C18—C19—C14	119.9 (3)
O1—C10—C9	125.5 (3)	C18—C19—H19	120.1
O2—C10—C9	111.1 (3)	C14—C19—H19	120.1
O2—C11—C12	107.1 (3)

C9—N1—N2—C7	−1.2 (3)	C13—N1—C9—C10	−9.9 (4)
C13—N1—N2—C7	−173.5 (2)	C7—C8—C9—N1	−0.2 (3)
C6—C1—C2—C3	0.0 (5)	C7—C8—C9—C10	−177.9 (3)
F1—C1—C2—C3	179.8 (3)	C11—O2—C10—O1	−0.3 (4)
C1—C2—C3—C4	−0.4 (5)	C11—O2—C10—C9	178.2 (2)
C2—C3—C4—C5	0.4 (4)	N1—C9—C10—O1	−6.4 (4)
C2—C3—C4—C7	180.0 (3)	C8—C9—C10—O1	171.0 (3)
C3—C4—C5—C6	0.0 (4)	N1—C9—C10—O2	175.1 (2)
C7—C4—C5—C6	−179.6 (2)	C8—C9—C10—O2	−7.4 (4)
C2—C1—C6—C5	0.4 (5)	C10—O2—C11—C12	−179.2 (3)
F1—C1—C6—C5	−179.4 (3)	N2—N1—C13—C14	94.7 (3)
C4—C5—C6—C1	−0.4 (5)	C9—N1—C13—C14	−76.1 (4)
N1—N2—C7—C8	1.0 (3)	N1—C13—C14—C15	128.1 (3)
N1—N2—C7—C4	−178.9 (2)	N1—C13—C14—C19	−52.8 (4)
C5—C4—C7—N2	4.6 (4)	C19—C14—C15—C16	−0.8 (4)
C3—C4—C7—N2	−175.0 (2)	C13—C14—C15—C16	178.3 (3)
C5—C4—C7—C8	−175.3 (3)	C14—C15—C16—C17	1.1 (5)
C3—C4—C7—C8	5.0 (4)	C15—C16—C17—C18	−0.4 (6)
N2—C7—C8—C9	−0.5 (3)	C16—C17—C18—C19	−0.6 (6)
C4—C7—C8—C9	179.4 (2)	C17—C18—C19—C14	0.9 (6)
N2—N1—C9—C8	0.8 (3)	C15—C14—C19—C18	−0.2 (5)
C13—N1—C9—C8	172.1 (3)	C13—C14—C19—C18	−179.3 (3)
N2—N1—C9—C10	178.8 (2)

Experimental details

Crystal data
Chemical formula	C₁₉H₁₇FN₂O₂
M_r	324.35
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.119 (8), 10.173 (6), 10.814 (6)
α, β, γ (°)	108.672 (15), 102.567 (16), 91.460 (16)
V (Å³)	821.5 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.21 × 0.16 × 0.12

Data collection
Diffractometer	Bruker SMART CD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.981, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	4034, 2844, 2014
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.084, 0.245, 1.07
No. of reflections	2844
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.30

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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