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

Li, Y.-Q.; Jia, B.-X.; Xiao, Y.-L.; Guo, F.-G.

doi:10.1107/S1600536811002339

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o468

doi:10.1107/S1600536811002339

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

Yu-Qin Li,^a Bao-Xiu Jia,^a Yu-Liang Xiao ^a ^* and Feng-Guang Guo ^a

^aTaishan Medical College, Tai an 271016, People's Republic of China
^*Correspondence e-mail: yqge@yahoo.cn

(Received 10 January 2011; accepted 16 January 2011; online 22 January 2011)

In the title compound, C₂₀H₂₀N₂O₂, the pyrazole ring makes dihedral angles of 15.68 (4) and 83.40 (4)°, respectively, with the tolyl and benzyl rings, respectively.

Related literature

For arelated structure, see: Ge et al. (2007 ). For applications of nitrogen-containing heterocyclic compounds in agrochemicals and pharmaceuticals, see: Ge et al. (2009a ,b , 2011 ).

Experimental

Crystal data

C₂₀H₂₀N₂O₂
M_r = 320.38
Triclinic, $[P \overline 1]$
a = 7.666 (4) Å
b = 10.160 (6) Å
c = 11.381 (7) Å
α = 83.991 (9)°
β = 87.466 (9)°
γ = 85.47 (1)°
V = 878.2 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.21 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.984, T_max = 0.991
4489 measured reflections
3045 independent reflections
2182 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.220
S = 1.06
3045 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.21 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/S1600536811002339/jh2257sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002339/jh2257Isup2.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.; 2011, 2009a, 2009b). Some pyrazole derivatives which belong to this category have been of interest for their biological activities. Considerable efforts have been devoted to the development of novel pyrazole compounds. We report here the crystal structure of the title compound, (I) (Fig. 1)

Related literature top

For arelated structure, see: Ge et al. (2007). For applications of nitrogen-containing heterocyclic compounds in agrochemicals and pharmaceuticals, see: Ge et al. (2009a,b, 2011). AUTHOR: remember to subdivide this section and to include all references

Experimental top

A mixture of ethyl 3-p-tolyl-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 82%). 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-methylphenyl)-1H-pyrazole-5-carboxylate top

Crystal data top

C₂₀H₂₀N₂O₂	Z = 2
M_r = 320.38	F(000) = 340
Triclinic, P1	D_x = 1.212 Mg m⁻³
a = 7.666 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.160 (6) Å	Cell parameters from 1778 reflections
c = 11.381 (7) Å	θ = 2.6–24.2°
α = 83.991 (9)°	µ = 0.08 mm⁻¹
β = 87.466 (9)°	T = 298 K
γ = 85.47 (1)°	BLOCK, white
V = 878.2 (9) Å³	0.21 × 0.16 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3045 independent reflections
Radiation source: fine-focus sealed tube	2182 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
phi and ω scans	θ_max = 25.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→8
T_min = 0.984, T_max = 0.991	k = −12→9
4489 measured reflections	l = −13→13

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.220	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.1348P)² + 0.1525P] where P = (F_o² + 2F_c²)/3
3045 reflections	(Δ/σ)_max < 0.001
217 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₀H₂₀N₂O₂	γ = 85.47 (1)°
M_r = 320.38	V = 878.2 (9) Å³
Triclinic, P1	Z = 2
a = 7.666 (4) Å	Mo Kα radiation
b = 10.160 (6) Å	µ = 0.08 mm⁻¹
c = 11.381 (7) Å	T = 298 K
α = 83.991 (9)°	0.21 × 0.16 × 0.12 mm
β = 87.466 (9)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3045 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	2182 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.991	R_int = 0.032
4489 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.220	H-atom parameters constrained
S = 1.06	Δρ_max = 0.34 e Å⁻³
3045 reflections	Δρ_min = −0.21 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
O1	0.3059 (3)	0.5585 (2)	0.70282 (17)	0.0826 (7)
O2	0.2483 (3)	0.6693 (2)	0.86211 (17)	0.0703 (6)
N1	0.3539 (3)	0.3185 (2)	0.86746 (18)	0.0548 (6)
N2	0.3537 (3)	0.2290 (2)	0.96361 (19)	0.0569 (6)
C1	0.1960 (6)	0.9004 (4)	0.8654 (3)	0.0955 (11)
H1A	0.1004	0.8824	0.9206	0.143*
H1B	0.1698	0.9836	0.8191	0.143*
H1C	0.3006	0.9049	0.9077	0.143*
C2	0.2227 (5)	0.7932 (3)	0.7865 (3)	0.0764 (9)
H2A	0.1213	0.7919	0.7387	0.092*
H2B	0.3246	0.8065	0.7342	0.092*
C3	0.2870 (3)	0.5601 (3)	0.8081 (2)	0.0597 (7)
C4	0.3021 (3)	0.4439 (3)	0.8954 (2)	0.0528 (6)
C5	0.2658 (3)	0.4323 (3)	1.0152 (2)	0.0551 (7)
H5	0.2268	0.5002	1.0609	0.066*
C6	0.2990 (3)	0.2986 (3)	1.0543 (2)	0.0517 (6)
C7	0.2828 (3)	0.2321 (3)	1.1751 (2)	0.0523 (6)
C8	0.2692 (4)	0.3059 (3)	1.2712 (2)	0.0625 (7)
H8	0.2707	0.3978	1.2586	0.075*
C9	0.2535 (4)	0.2459 (3)	1.3851 (2)	0.0669 (8)
H9	0.2442	0.2982	1.4478	0.080*
C10	0.2512 (4)	0.1096 (3)	1.4083 (2)	0.0616 (7)
C11	0.2643 (4)	0.0367 (3)	1.3121 (3)	0.0717 (8)
H11	0.2620	−0.0551	1.3247	0.086*
C12	0.2806 (4)	0.0958 (3)	1.1980 (2)	0.0648 (8)
H12	0.2903	0.0433	1.1355	0.078*
C13	0.2361 (5)	0.0423 (4)	1.5327 (3)	0.0880 (10)
H13A	0.2140	−0.0490	1.5301	0.132*
H13B	0.1414	0.0861	1.5752	0.132*
H13C	0.3434	0.0471	1.5719	0.132*
C14	0.4189 (3)	0.2742 (3)	0.7545 (2)	0.0608 (7)
H14A	0.3443	0.3163	0.6925	0.073*
H14B	0.4110	0.1791	0.7574	0.073*
C15	0.6048 (3)	0.3050 (2)	0.7234 (2)	0.0485 (6)
C16	0.6535 (4)	0.3469 (3)	0.6073 (2)	0.0596 (7)
H16	0.5692	0.3606	0.5501	0.071*
C17	0.8246 (4)	0.3682 (3)	0.5762 (3)	0.0730 (9)
H17	0.8563	0.3945	0.4979	0.088*
C18	0.9483 (4)	0.3509 (4)	0.6601 (3)	0.0766 (9)
H18	1.0637	0.3675	0.6390	0.092*
C19	0.9039 (4)	0.3090 (3)	0.7758 (3)	0.0692 (8)
H19	0.9892	0.2966	0.8324	0.083*
C20	0.7326 (3)	0.2855 (3)	0.8074 (2)	0.0555 (7)
H20	0.7025	0.2566	0.8853	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1089 (17)	0.0879 (17)	0.0500 (12)	−0.0083 (13)	−0.0052 (10)	−0.0005 (11)
O2	0.0972 (15)	0.0575 (12)	0.0542 (11)	−0.0067 (10)	−0.0058 (9)	0.0058 (9)
N1	0.0577 (12)	0.0589 (14)	0.0494 (12)	−0.0112 (10)	0.0018 (9)	−0.0093 (10)
N2	0.0608 (13)	0.0548 (13)	0.0561 (13)	−0.0100 (10)	0.0022 (10)	−0.0083 (10)
C1	0.131 (3)	0.061 (2)	0.091 (2)	−0.0049 (19)	−0.015 (2)	0.0112 (18)
C2	0.091 (2)	0.065 (2)	0.0695 (19)	−0.0083 (16)	−0.0136 (16)	0.0169 (16)
C3	0.0604 (16)	0.0674 (18)	0.0520 (16)	−0.0112 (13)	−0.0059 (11)	−0.0031 (13)
C4	0.0542 (14)	0.0551 (16)	0.0501 (14)	−0.0110 (11)	−0.0027 (11)	−0.0037 (12)
C5	0.0643 (16)	0.0517 (15)	0.0500 (14)	−0.0065 (12)	0.0008 (11)	−0.0082 (11)
C6	0.0545 (14)	0.0512 (15)	0.0509 (14)	−0.0089 (11)	0.0025 (11)	−0.0098 (11)
C7	0.0545 (14)	0.0491 (15)	0.0531 (14)	−0.0051 (11)	0.0026 (11)	−0.0056 (11)
C8	0.0851 (19)	0.0470 (15)	0.0561 (16)	−0.0106 (13)	0.0011 (13)	−0.0061 (12)
C9	0.089 (2)	0.0595 (18)	0.0530 (16)	−0.0082 (15)	0.0023 (14)	−0.0104 (13)
C10	0.0716 (17)	0.0582 (17)	0.0534 (15)	−0.0028 (13)	0.0007 (12)	−0.0007 (12)
C11	0.103 (2)	0.0443 (16)	0.0660 (18)	−0.0029 (14)	0.0045 (16)	−0.0023 (13)
C12	0.091 (2)	0.0462 (15)	0.0567 (16)	−0.0007 (13)	0.0029 (14)	−0.0081 (12)
C13	0.123 (3)	0.079 (2)	0.0594 (19)	−0.008 (2)	−0.0044 (18)	0.0073 (16)
C14	0.0632 (16)	0.0726 (19)	0.0512 (14)	−0.0156 (13)	−0.0016 (12)	−0.0198 (13)
C15	0.0543 (14)	0.0459 (14)	0.0472 (13)	−0.0054 (10)	−0.0033 (10)	−0.0120 (10)
C16	0.0669 (17)	0.0637 (17)	0.0481 (14)	−0.0030 (13)	−0.0076 (12)	−0.0048 (12)
C17	0.0712 (19)	0.087 (2)	0.0594 (17)	−0.0095 (16)	0.0107 (14)	−0.0026 (15)
C18	0.0563 (17)	0.092 (2)	0.081 (2)	−0.0046 (15)	0.0081 (15)	−0.0122 (18)
C19	0.0549 (16)	0.084 (2)	0.0699 (18)	0.0027 (14)	−0.0142 (13)	−0.0154 (16)
C20	0.0669 (16)	0.0551 (15)	0.0456 (13)	−0.0038 (12)	−0.0063 (11)	−0.0096 (11)

Geometric parameters (Å, º) top

O1—C3	1.202 (3)	C9—H9	0.9300
O2—C3	1.332 (3)	C10—C11	1.381 (4)
O2—C2	1.453 (3)	C10—C13	1.510 (4)
N1—N2	1.348 (3)	C11—C12	1.376 (4)
N1—C4	1.369 (3)	C11—H11	0.9300
N1—C14	1.461 (3)	C12—H12	0.9300
N2—C6	1.345 (3)	C13—H13A	0.9600
C1—C2	1.480 (5)	C13—H13B	0.9600
C1—H1A	0.9600	C13—H13C	0.9600
C1—H1B	0.9600	C14—C15	1.502 (3)
C1—H1C	0.9600	C14—H14A	0.9700
C2—H2A	0.9700	C14—H14B	0.9700
C2—H2B	0.9700	C15—C20	1.388 (4)
C3—C4	1.463 (4)	C15—C16	1.389 (4)
C4—C5	1.374 (3)	C16—C17	1.372 (4)
C5—C6	1.392 (4)	C16—H16	0.9300
C5—H5	0.9300	C17—C18	1.364 (4)
C6—C7	1.471 (4)	C17—H17	0.9300
C7—C12	1.384 (4)	C18—C19	1.377 (4)
C7—C8	1.386 (4)	C18—H18	0.9300
C8—C9	1.378 (4)	C19—C20	1.379 (4)
C8—H8	0.9300	C19—H19	0.9300
C9—C10	1.384 (4)	C20—H20	0.9300

C3—O2—C2	116.6 (2)	C11—C10—C13	121.0 (3)
N2—N1—C4	111.8 (2)	C9—C10—C13	122.1 (3)
N2—N1—C14	118.5 (2)	C12—C11—C10	122.0 (3)
C4—N1—C14	129.5 (2)	C12—C11—H11	119.0
C6—N2—N1	105.3 (2)	C10—C11—H11	119.0
C2—C1—H1A	109.5	C11—C12—C7	121.0 (3)
C2—C1—H1B	109.5	C11—C12—H12	119.5
H1A—C1—H1B	109.5	C7—C12—H12	119.5
C2—C1—H1C	109.5	C10—C13—H13A	109.5
H1A—C1—H1C	109.5	C10—C13—H13B	109.5
H1B—C1—H1C	109.5	H13A—C13—H13B	109.5
O2—C2—C1	106.8 (3)	C10—C13—H13C	109.5
O2—C2—H2A	110.4	H13A—C13—H13C	109.5
C1—C2—H2A	110.4	H13B—C13—H13C	109.5
O2—C2—H2B	110.4	N1—C14—C15	113.41 (19)
C1—C2—H2B	110.4	N1—C14—H14A	108.9
H2A—C2—H2B	108.6	C15—C14—H14A	108.9
O1—C3—O2	124.5 (3)	N1—C14—H14B	108.9
O1—C3—C4	125.5 (3)	C15—C14—H14B	108.9
O2—C3—C4	110.0 (2)	H14A—C14—H14B	107.7
N1—C4—C5	106.1 (2)	C20—C15—C16	118.7 (2)
N1—C4—C3	123.6 (2)	C20—C15—C14	121.2 (2)
C5—C4—C3	130.3 (3)	C16—C15—C14	119.9 (2)
C4—C5—C6	106.2 (2)	C17—C16—C15	120.7 (2)
C4—C5—H5	126.9	C17—C16—H16	119.7
C6—C5—H5	126.9	C15—C16—H16	119.7
N2—C6—C5	110.6 (2)	C18—C17—C16	119.9 (3)
N2—C6—C7	120.6 (2)	C18—C17—H17	120.0
C5—C6—C7	128.8 (2)	C16—C17—H17	120.0
C12—C7—C8	117.3 (2)	C17—C18—C19	120.6 (3)
C12—C7—C6	122.4 (2)	C17—C18—H18	119.7
C8—C7—C6	120.2 (2)	C19—C18—H18	119.7
C9—C8—C7	121.3 (3)	C18—C19—C20	119.7 (3)
C9—C8—H8	119.4	C18—C19—H19	120.1
C7—C8—H8	119.4	C20—C19—H19	120.1
C8—C9—C10	121.5 (3)	C19—C20—C15	120.3 (2)
C8—C9—H9	119.3	C19—C20—H20	119.9
C10—C9—H9	119.3	C15—C20—H20	119.9
C11—C10—C9	116.9 (3)

C4—N1—N2—C6	0.6 (3)	C12—C7—C8—C9	−0.2 (4)
C14—N1—N2—C6	176.1 (2)	C6—C7—C8—C9	179.8 (2)
C3—O2—C2—C1	−175.4 (3)	C7—C8—C9—C10	0.2 (5)
C2—O2—C3—O1	1.8 (4)	C8—C9—C10—C11	−0.4 (5)
C2—O2—C3—C4	−177.9 (2)	C8—C9—C10—C13	179.3 (3)
N2—N1—C4—C5	−0.6 (3)	C9—C10—C11—C12	0.6 (5)
C14—N1—C4—C5	−175.4 (2)	C13—C10—C11—C12	−179.1 (3)
N2—N1—C4—C3	−178.8 (2)	C10—C11—C12—C7	−0.7 (5)
C14—N1—C4—C3	6.4 (4)	C8—C7—C12—C11	0.4 (4)
O1—C3—C4—N1	5.4 (4)	C6—C7—C12—C11	−179.6 (3)
O2—C3—C4—N1	−174.9 (2)	N2—N1—C14—C15	−99.0 (3)
O1—C3—C4—C5	−172.3 (3)	C4—N1—C14—C15	75.5 (3)
O2—C3—C4—C5	7.4 (4)	N1—C14—C15—C20	42.9 (4)
N1—C4—C5—C6	0.4 (3)	N1—C14—C15—C16	−140.7 (3)
C3—C4—C5—C6	178.4 (2)	C20—C15—C16—C17	0.2 (4)
N1—N2—C6—C5	−0.4 (3)	C14—C15—C16—C17	−176.3 (3)
N1—N2—C6—C7	−179.9 (2)	C15—C16—C17—C18	−1.3 (5)
C4—C5—C6—N2	0.0 (3)	C16—C17—C18—C19	1.5 (5)
C4—C5—C6—C7	179.5 (2)	C17—C18—C19—C20	−0.6 (5)
N2—C6—C7—C12	−16.0 (4)	C18—C19—C20—C15	−0.5 (4)
C5—C6—C7—C12	164.6 (3)	C16—C15—C20—C19	0.7 (4)
N2—C6—C7—C8	164.0 (2)	C14—C15—C20—C19	177.2 (2)
C5—C6—C7—C8	−15.4 (4)

Experimental details

Crystal data
Chemical formula	C₂₀H₂₀N₂O₂
M_r	320.38
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.666 (4), 10.160 (6), 11.381 (7)
α, β, γ (°)	83.991 (9), 87.466 (9), 85.47 (1)
V (Å³)	878.2 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.21 × 0.16 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.984, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	4489, 3045, 2182
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.220, 1.06
No. of reflections	3045
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.21

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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Ge, Y. Q., Jia, J., Li, Y., Yin, L. & Wang, J. W. (2009a). Heterocycles, 42, 197–206. Google Scholar
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