Ethyl 1-benzyl-3-phenyl-1H-pyrazole-5-carboxyl­ate

Xia, Y.; Dong, W.-L.; Ding, X.-L.; Zhao, B.-X.

doi:10.1107/S1600536807030139

Ethyl 1-benzyl-3-phenyl-1H-pyrazole-5-carboxylate

Y. Xia, W.-L. Dong, X.-L. Ding and B.-X. Zhao

In the title compound, C₁₉H₁₈N₂O₂, the dihedral angles made by the central pyrazole ring with the benzyl and phenyl rings are 87.00 (9) and 15.23 (9)°, respectively. There is a short intermolecular interaction between a C-H bond and the benzyl ring.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030139/bg2070sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030139/bg2070Isup2.hkl Contains datablock I

CCDC reference: 655021

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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 = 18.0

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No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     -   C7      ..       5.31 su

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
   1 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
   1 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
   0 ALERT type 5 Informative message, check

Comment top

The pyrazole unit is one of the core structures in a number of natural products. Pyrazole derivatives have a broad spectrum of biological activities being used as antidiabetic (Cottineau et al., 2006), antitumour (Wei et al., 2006), antithrombotic (Qiao et al., 2007), gastric secretion stimulatory, antidepressant and against rheumatoid arthritis agents. Many of them are also currently being used as herbicides, fungicides, pesticides, insecticides and dyestuffs, in sunscreen materials and as analytical reagents (Singh et al., 2006). We report here the crystal structure of the title compound C₁₉H₁₈N₂O₂ (I) (Fig. 1). The most relevant features in the structure are the dihedral angles made by the central pyrazole ring and the lateral benzyl and phenyl rings, which amount 87.00 (9)° and 15.23 (9)°, respectively. There is a short C3—H3···Cgⁱ intermolecular interaction in the structure, where (i): 1 - x,1 - y,-z and Cg: the centroid of the benzyl ring.

Related literature top

For related literature, see: Altomare et al. (1999); Cottineau et al. (2006); Farrugia (1999); Qiao et al. (2007); Singh et al. (2006); Wei et al. (2006); Xia et al. (2007).

Experimental top

The compound was synthesized according to the literature procedure (Xia et al., 2007). Crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid in ethyl acetate/petroleum ether (1:2 v/v) at room temperature over a period of 4 d.

Structure description top

For related literature, see: Altomare et al. (1999); Cottineau et al. (2006); Farrugia (1999); Qiao et al. (2007); Singh et al. (2006); Wei et al. (2006); Xia et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: WinGX (Farrugia,1999).

Figures top

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

Ethyl 1-benzyl-3-phenyl-1H-pyrazole-5-carboxylate top

Crystal data top

C₁₉H₁₈N₂O₂	F(000) = 1296
M_r = 306.35	D_x = 1.236 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2989 reflections
a = 10.7352 (2) Å	θ = 2.5–20.6°
b = 14.9914 (2) Å	µ = 0.08 mm⁻¹
c = 20.4561 (3) Å	T = 293 K
V = 3292.12 (9) Å³	Prism, colourless
Z = 8	0.28 × 0.22 × 0.20 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	3753 independent reflections
Radiation source: fine-focus sealed tube	1983 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 27.5°, θ_min = 2.0°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −12→13
T_min = 0.95, T_max = 0.98	k = −14→19
14925 measured reflections	l = −23→26

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 = 0.98	w = 1/[σ²(F_o²) + (0.0447P)² + 0.4671P] where P = (F_o² + 2F_c²)/3
3753 reflections	(Δ/σ)_max < 0.001
209 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₉H₁₈N₂O₂	V = 3292.12 (9) Å³
M_r = 306.35	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.7352 (2) Å	µ = 0.08 mm⁻¹
b = 14.9914 (2) Å	T = 293 K
c = 20.4561 (3) Å	0.28 × 0.22 × 0.20 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	3753 independent reflections
Absorption correction: multi-scan (APEX2; Bruker, 2005)	1983 reflections with I > 2σ(I)
T_min = 0.95, T_max = 0.98	R_int = 0.030
14925 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 0.98	Δρ_max = 0.17 e Å⁻³
3753 reflections	Δρ_min = −0.16 e Å⁻³
209 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	0.4305 (3)	0.23696 (14)	0.25853 (11)	0.0897 (7)
H1	0.4039	0.2536	0.2170	0.108*
C2	0.3550 (2)	0.18657 (14)	0.29793 (11)	0.0831 (6)
H2	0.2768	0.1692	0.2830	0.100*
C3	0.39371 (19)	0.16145 (12)	0.35920 (10)	0.0692 (5)
H3	0.3415	0.1272	0.3854	0.083*
C4	0.50986 (17)	0.18666 (10)	0.38243 (9)	0.0579 (4)
C5	0.5860 (2)	0.23772 (12)	0.34255 (10)	0.0745 (5)
H5	0.6642	0.2552	0.3572	0.089*
C6	0.5459 (2)	0.26281 (14)	0.28082 (11)	0.0893 (7)
H6	0.5972	0.2973	0.2543	0.107*
C7	0.55031 (16)	0.16023 (10)	0.44805 (8)	0.0546 (4)
C8	0.47946 (16)	0.12737 (11)	0.49970 (8)	0.0578 (4)
H8	0.3941	0.1167	0.4998	0.069*
C9	0.56075 (16)	0.11390 (10)	0.55025 (8)	0.0556 (4)
C10	0.5378 (2)	0.08303 (11)	0.61744 (9)	0.0628 (5)
C11	0.3818 (2)	0.02637 (14)	0.68818 (9)	0.0815 (6)
H11A	0.3969	0.0722	0.7207	0.098*
H11B	0.4288	−0.0264	0.7002	0.098*
C12	0.2485 (2)	0.00559 (17)	0.68466 (12)	0.1118 (8)
H12A	0.2037	0.0571	0.6696	0.168*
H12B	0.2189	−0.0110	0.7272	0.168*
H12C	0.2355	−0.0429	0.6548	0.168*
C13	0.79636 (15)	0.13233 (11)	0.56062 (9)	0.0628 (5)
H13A	0.7897	0.1571	0.6043	0.075*
H13B	0.8565	0.1678	0.5366	0.075*
C14	0.84326 (14)	0.03803 (11)	0.56537 (8)	0.0544 (4)
C15	0.89934 (18)	0.00852 (14)	0.62189 (10)	0.0741 (5)
H15	0.9054	0.0466	0.6577	0.089*
C16	0.9465 (2)	−0.07644 (17)	0.62605 (13)	0.0942 (7)
H16	0.9847	−0.0954	0.6644	0.113*
C17	0.9375 (2)	−0.13319 (15)	0.57405 (15)	0.0940 (7)
H17	0.9694	−0.1907	0.5770	0.113*
C18	0.88155 (19)	−0.10520 (14)	0.51756 (12)	0.0826 (6)
H18	0.8748	−0.1439	0.4822	0.099*
C19	0.83502 (16)	−0.01959 (12)	0.51301 (9)	0.0642 (5)
H19	0.7979	−0.0006	0.4744	0.077*
N1	0.67075 (13)	0.16654 (8)	0.46589 (7)	0.0592 (4)
N2	0.67539 (12)	0.13894 (8)	0.52832 (7)	0.0559 (4)
O1	0.61277 (14)	0.08151 (10)	0.66085 (6)	0.0862 (4)
O2	0.41949 (12)	0.05760 (9)	0.62380 (6)	0.0762 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.126 (2)	0.0814 (15)	0.0617 (14)	0.0286 (15)	−0.0070 (14)	−0.0002 (12)
C2	0.1004 (16)	0.0739 (13)	0.0749 (15)	0.0142 (12)	−0.0148 (13)	−0.0095 (12)
C3	0.0794 (13)	0.0613 (11)	0.0668 (13)	0.0047 (9)	−0.0005 (10)	−0.0043 (9)
C4	0.0701 (12)	0.0466 (9)	0.0570 (11)	0.0106 (9)	0.0082 (9)	−0.0004 (8)
C5	0.0825 (14)	0.0720 (12)	0.0691 (14)	0.0079 (10)	0.0102 (11)	0.0132 (10)
C6	0.1150 (19)	0.0806 (14)	0.0722 (15)	0.0160 (14)	0.0191 (14)	0.0187 (12)
C7	0.0592 (10)	0.0445 (9)	0.0600 (11)	0.0031 (7)	0.0060 (9)	−0.0019 (8)
C8	0.0552 (10)	0.0552 (10)	0.0630 (11)	−0.0004 (8)	0.0054 (9)	−0.0004 (8)
C9	0.0624 (11)	0.0462 (9)	0.0583 (11)	−0.0015 (8)	0.0062 (9)	−0.0035 (8)
C10	0.0771 (14)	0.0547 (10)	0.0566 (12)	0.0002 (9)	0.0061 (10)	−0.0069 (9)
C11	0.1074 (17)	0.0797 (13)	0.0574 (12)	−0.0056 (12)	0.0229 (11)	0.0042 (10)
C12	0.1035 (18)	0.138 (2)	0.0938 (18)	−0.0042 (16)	0.0361 (14)	0.0293 (15)
C13	0.0612 (11)	0.0553 (10)	0.0719 (13)	−0.0078 (8)	−0.0047 (9)	−0.0068 (9)
C14	0.0493 (9)	0.0546 (10)	0.0593 (11)	−0.0057 (8)	−0.0004 (8)	−0.0017 (8)
C15	0.0749 (13)	0.0791 (13)	0.0683 (13)	−0.0028 (11)	−0.0092 (10)	0.0024 (10)
C16	0.0843 (16)	0.0905 (17)	0.108 (2)	0.0080 (13)	−0.0148 (14)	0.0280 (15)
C17	0.0756 (15)	0.0621 (13)	0.144 (2)	0.0085 (11)	0.0097 (15)	0.0158 (16)
C18	0.0742 (14)	0.0639 (13)	0.1098 (18)	−0.0034 (10)	0.0115 (13)	−0.0203 (12)
C19	0.0626 (11)	0.0598 (12)	0.0703 (13)	−0.0057 (9)	−0.0001 (9)	−0.0082 (9)
N1	0.0664 (10)	0.0493 (8)	0.0619 (10)	0.0002 (7)	0.0075 (7)	0.0044 (7)
N2	0.0578 (9)	0.0475 (8)	0.0623 (9)	−0.0007 (6)	0.0007 (7)	−0.0017 (7)
O1	0.0895 (10)	0.1121 (11)	0.0569 (9)	−0.0023 (8)	−0.0046 (8)	−0.0046 (8)
O2	0.0781 (9)	0.0909 (9)	0.0597 (9)	−0.0135 (7)	0.0103 (7)	0.0107 (7)

Geometric parameters (Å, º) top

C1—C2	1.370 (3)	C11—H11A	0.9700
C1—C6	1.375 (3)	C11—H11B	0.9700
C1—H1	0.9300	C12—H12A	0.9600
C2—C3	1.373 (3)	C12—H12B	0.9600
C2—H2	0.9300	C12—H12C	0.9600
C3—C4	1.387 (2)	C13—N2	1.460 (2)
C3—H3	0.9300	C13—C14	1.504 (2)
C4—C5	1.385 (2)	C13—H13A	0.9700
C4—C7	1.465 (2)	C13—H13B	0.9700
C5—C6	1.386 (3)	C14—C15	1.376 (2)
C5—H5	0.9300	C14—C19	1.379 (2)
C6—H6	0.9300	C15—C16	1.373 (3)
C7—N1	1.347 (2)	C15—H15	0.9300
C7—C8	1.392 (2)	C16—C17	1.366 (3)
C8—C9	1.368 (2)	C16—H16	0.9300
C8—H8	0.9300	C17—C18	1.368 (3)
C9—N2	1.363 (2)	C17—H17	0.9300
C9—C10	1.471 (2)	C18—C19	1.380 (3)
C10—O1	1.198 (2)	C18—H18	0.9300
C10—O2	1.333 (2)	C19—H19	0.9300
C11—O2	1.455 (2)	N1—N2	1.3433 (19)
C11—C12	1.467 (3)

C2—C1—C6	119.5 (2)	C11—C12—H12A	109.5
C2—C1—H1	120.2	C11—C12—H12B	109.5
C6—C1—H1	120.2	H12A—C12—H12B	109.5
C1—C2—C3	120.6 (2)	C11—C12—H12C	109.5
C1—C2—H2	119.7	H12A—C12—H12C	109.5
C3—C2—H2	119.7	H12B—C12—H12C	109.5
C2—C3—C4	120.67 (19)	N2—C13—C14	113.00 (13)
C2—C3—H3	119.7	N2—C13—H13A	109.0
C4—C3—H3	119.7	C14—C13—H13A	109.0
C3—C4—C5	118.63 (18)	N2—C13—H13B	109.0
C3—C4—C7	120.43 (16)	C14—C13—H13B	109.0
C5—C4—C7	120.94 (17)	H13A—C13—H13B	107.8
C4—C5—C6	120.2 (2)	C15—C14—C19	118.63 (17)
C4—C5—H5	119.9	C15—C14—C13	120.18 (16)
C6—C5—H5	119.9	C19—C14—C13	121.15 (16)
C1—C6—C5	120.3 (2)	C14—C15—C16	120.8 (2)
C1—C6—H6	119.8	C14—C15—H15	119.6
C5—C6—H6	119.8	C16—C15—H15	119.6
N1—C7—C8	110.11 (15)	C17—C16—C15	120.2 (2)
N1—C7—C4	120.91 (15)	C17—C16—H16	119.9
C8—C7—C4	128.98 (16)	C15—C16—H16	119.9
C9—C8—C7	106.11 (16)	C18—C17—C16	119.8 (2)
C9—C8—H8	126.9	C18—C17—H17	120.1
C7—C8—H8	126.9	C16—C17—H17	120.1
N2—C9—C8	106.65 (15)	C17—C18—C19	120.1 (2)
N2—C9—C10	123.05 (16)	C17—C18—H18	120.0
C8—C9—C10	130.24 (17)	C19—C18—H18	120.0
O1—C10—O2	124.21 (18)	C14—C19—C18	120.45 (19)
O1—C10—C9	125.87 (18)	C14—C19—H19	119.8
O2—C10—C9	109.91 (17)	C18—C19—H19	119.8
O2—C11—C12	107.16 (18)	C7—N1—N2	105.76 (13)
O2—C11—H11A	110.3	N1—N2—C9	111.37 (13)
C12—C11—H11A	110.3	N1—N2—C13	118.95 (13)
O2—C11—H11B	110.3	C9—N2—C13	129.45 (15)
C12—C11—H11B	110.3	C10—O2—C11	116.43 (16)
H11A—C11—H11B	108.5

C6—C1—C2—C3	−0.3 (3)	C19—C14—C15—C16	0.2 (3)
C1—C2—C3—C4	0.1 (3)	C13—C14—C15—C16	−177.69 (17)
C2—C3—C4—C5	0.0 (3)	C14—C15—C16—C17	−0.4 (3)
C2—C3—C4—C7	179.54 (16)	C15—C16—C17—C18	0.1 (3)
C3—C4—C5—C6	0.1 (3)	C16—C17—C18—C19	0.5 (3)
C7—C4—C5—C6	−179.44 (17)	C15—C14—C19—C18	0.4 (3)
C2—C1—C6—C5	0.4 (3)	C13—C14—C19—C18	178.24 (16)
C4—C5—C6—C1	−0.3 (3)	C17—C18—C19—C14	−0.7 (3)
C3—C4—C7—N1	165.11 (15)	C8—C7—N1—N2	−0.70 (17)
C5—C4—C7—N1	−15.4 (2)	C4—C7—N1—N2	178.93 (13)
C3—C4—C7—C8	−15.3 (2)	C7—N1—N2—C9	0.95 (17)
C5—C4—C7—C8	164.16 (17)	C7—N1—N2—C13	175.92 (13)
N1—C7—C8—C9	0.20 (18)	C8—C9—N2—N1	−0.84 (17)
C4—C7—C8—C9	−179.39 (15)	C10—C9—N2—N1	−178.36 (14)
C7—C8—C9—N2	0.37 (17)	C8—C9—N2—C13	−175.13 (14)
C7—C8—C9—C10	177.64 (16)	C10—C9—N2—C13	7.4 (2)
N2—C9—C10—O1	4.9 (3)	C14—C13—N2—N1	−102.49 (17)
C8—C9—C10—O1	−171.99 (18)	C14—C13—N2—C9	71.4 (2)
N2—C9—C10—O2	−175.95 (14)	O1—C10—O2—C11	0.0 (3)
C8—C9—C10—O2	7.2 (2)	C9—C10—O2—C11	−179.15 (14)
N2—C13—C14—C15	−138.32 (16)	C12—C11—O2—C10	177.76 (17)
N2—C13—C14—C19	43.9 (2)

Experimental details

Crystal data
Chemical formula	C₁₉H₁₈N₂O₂
M_r	306.35
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	10.7352 (2), 14.9914 (2), 20.4561 (3)
V (Å³)	3292.12 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.28 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (APEX2; Bruker, 2005)
T_min, T_max	0.95, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	14925, 3753, 1983
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.120, 0.98
No. of reflections	3753
No. of parameters	209
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.16

Computer programs: APEX2 (Bruker, 2005), APEX2, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), WinGX (Farrugia,1999).

X—H···π ring interactions top

X—H···Cg	X—H	H···Cg	X···Cg	X—H···Cg
C3—H3···Cg3ⁱ	0.93	2.91	3.785 (2)	157

Symmetry code: (i) 1-x, 1-y, -z. Values were calculated by PLATON (Spek, 2003). Cg is the centroid of the benzyl ring C14–C19.

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Ethyl 1-benzyl-3-phenyl-1H-pyrazole-5-carboxyl­ate

Supporting information

Key indicators

checkCIF/PLATON results

Ethyl 1-benzyl-3-phenyl-1H-pyrazole-5-carboxylate