3-(5-Oxo-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)benzonitrile

Li, L.; Tong, R.; Li, J.; Shi, J.

doi:10.1107/S1600536812027444

organic compounds

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Volume 68| Part 7| July 2012| Page o2230

https://doi.org/10.1107/S1600536812027444

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3-(5-Oxo-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)benzonitrile

Ling Li,^a Rong-sheng Tong,^b Jin-qi Li ^b and Jian-you Shi ^b ^*

^aBioengineering College, Xihua University, Sichuan Provincial, People's Hospital, Chengdu 610039, People's Republic of China, and ^bDepartment of Pharmacy, Sichuan Academy of Medical Science and Sichuan Provincial, People's Hospital, Chengdu 610072, People's Republic of China
^*Correspondence e-mail: shijianyoude@126.com

(Received 31 May 2012; accepted 17 June 2012; online 27 June 2012)

In the title compound, C₁₆H₁₁N₃O, the dihedral angles between the 3-cyanobenzene and benzene planes and the 1H-pyrazol-5(4H)-one plane are 4.97 (9) and 9.91 (9)°, respectively.

Related literature

For a similar structure, see: Paulis et al. (2006 ).

Experimental

Crystal data

C₁₆H₁₁N₃O
M_r = 261.28
Monoclinic, P 2₁ /c
a = 7.6683 (3) Å
b = 17.8013 (7) Å
c = 9.7574 (4) Å
β = 106.506 (4)°
V = 1277.05 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.34 × 0.30 × 0.28 mm

Data collection

Agilent Xcalibur diffractometer with an Eos CCD detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.967, T_max = 1.000
5145 measured reflections
2608 independent reflections
1686 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.119
S = 1.02
2608 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: OLEX2.solve (Bourhis et al., 2012 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812027444/zs2212sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027444/zs2212Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812027444/zs2212Isup3.cml

checkCIF report

Comment top

In our research, 1,3-Diphenyl-1H-pyrazol-5(4H)-one is a member of a series of compounds which are being investigated for their potential as anticancer agents. In the analogous title compound, C₁₆H₁₁N₃O, (Fig. 1), the dihedral angles between the 3-cyanobenzene and benzene planes and the 1H-pyrazol-5(4)-one plane are 4.97 (9)° and 9.91 (9)°, respectively. Present also in the structure are intramolecular aromatic C—H···N and C—H···O interactions (Table 1). A similar structure has been peviously been reported (Paulis et al., 2006).

Related literature top

For a similar structure, see: Paulis et al. (2006).

Experimental top

A mixture of 3-hydrazinylbenzonitrile hydrochloride (1.96 g, 0.01 mol) and ethyl 3-oxo-3-phenylpropanoate (1.92 g, 0.01 mol) in acetic acid (50 mL) was heated under reflux for 1.5 h, then poured into ice water. The precipitated product was filtered, giving the title compound as a powder. Single crystals were by obtained by room temperature evaporation of a solution in CH₂Cl₂–MeOH after 5 days.

Structure description top

For a similar structure, see: Paulis et al. (2006).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: OLEX2.solve (Bourhis et al., 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

Fig. 1. The molecular structure of title compound showing atom numbering, with displacement ellipsoids drawn at the 40% probability level.

3-(5-Oxo-3-phenyl-4,5-dihydro-1H-pyrazol-1-yl)benzonitrile top

Crystal data top

C₁₆H₁₁N₃O	F(000) = 544
M_r = 261.28	D_x = 1.359 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
a = 7.6683 (3) Å	Cell parameters from 1663 reflections
b = 17.8013 (7) Å	θ = 3.0–29.1°
c = 9.7574 (4) Å	µ = 0.09 mm⁻¹
β = 106.506 (4)°	T = 293 K
V = 1277.05 (9) Å³	Block, orange
Z = 4	0.34 × 0.30 × 0.28 mm

Data collection top

Agilent Xcalibur diffractometer with an Eos CCD detector	2608 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1686 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 16.0874 pixels mm^-1	θ_max = 26.4°, θ_min = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→22
T_min = 0.967, T_max = 1.000	l = −12→11
5145 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0461P)² + 0.0009P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
2608 reflections	Δρ_max = 0.14 e Å⁻³
182 parameters	Δρ_min = −0.13 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0083 (15)

Crystal data top

C₁₆H₁₁N₃O	V = 1277.05 (9) Å³
M_r = 261.28	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.6683 (3) Å	µ = 0.09 mm⁻¹
b = 17.8013 (7) Å	T = 293 K
c = 9.7574 (4) Å	0.34 × 0.30 × 0.28 mm
β = 106.506 (4)°

Data collection top

Agilent Xcalibur diffractometer with an Eos CCD detector	2608 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1686 reflections with I > 2σ(I)
T_min = 0.967, T_max = 1.000	R_int = 0.023
5145 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.02	Δρ_max = 0.14 e Å⁻³
2608 reflections	Δρ_min = −0.13 e Å⁻³
182 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	0.10361 (18)	0.26129 (9)	0.88140 (16)	0.0787 (5)
N1	−0.4410 (2)	0.40574 (12)	1.0212 (2)	0.0843 (6)
N2	0.14347 (17)	0.36652 (9)	0.75427 (15)	0.0460 (4)
N3	0.25680 (17)	0.38881 (9)	0.67037 (14)	0.0453 (4)
C1	−0.2203 (2)	0.45145 (12)	0.88230 (18)	0.0505 (5)
C2	−0.2216 (2)	0.52432 (12)	0.8356 (2)	0.0588 (5)
H2	−0.3015	0.5594	0.8547	0.071*
C3	−0.1018 (2)	0.54437 (13)	0.7599 (2)	0.0658 (6)
H3	−0.1013	0.5934	0.7272	0.079*
C4	0.0173 (2)	0.49230 (12)	0.7321 (2)	0.0574 (5)
H4	0.0964	0.5064	0.6800	0.069*
C5	0.0196 (2)	0.41964 (11)	0.78127 (17)	0.0446 (5)
C6	−0.1013 (2)	0.39869 (12)	0.85627 (17)	0.0502 (5)
H6	−0.1024	0.3496	0.8888	0.060*
C7	−0.3450 (2)	0.42714 (12)	0.9599 (2)	0.0597 (6)
C8	0.1780 (2)	0.29424 (12)	0.8051 (2)	0.0521 (5)
C9	0.3237 (2)	0.26591 (11)	0.7431 (2)	0.0535 (5)
H9A	0.4313	0.2508	0.8176	0.064*
H9B	0.2809	0.2239	0.6791	0.064*
C10	0.3602 (2)	0.33246 (10)	0.66476 (16)	0.0413 (4)
C11	0.4987 (2)	0.33671 (10)	0.58749 (17)	0.0415 (4)
C12	0.6261 (2)	0.27999 (12)	0.60224 (19)	0.0518 (5)
H12	0.6224	0.2387	0.6598	0.062*
C13	0.7591 (2)	0.28432 (12)	0.5318 (2)	0.0574 (6)
H13	0.8448	0.2462	0.5428	0.069*
C14	0.7649 (2)	0.34450 (13)	0.4461 (2)	0.0622 (6)
H14	0.8542	0.3472	0.3987	0.075*
C15	0.6379 (2)	0.40112 (12)	0.4301 (2)	0.0627 (6)
H15	0.6411	0.4420	0.3714	0.075*
C16	0.5064 (2)	0.39714 (11)	0.50101 (19)	0.0527 (5)
H16	0.4218	0.4357	0.4904	0.063*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0755 (9)	0.0780 (12)	0.1024 (11)	0.0167 (8)	0.0571 (9)	0.0415 (10)
N1	0.0917 (12)	0.0754 (15)	0.1115 (14)	0.0126 (11)	0.0702 (12)	0.0119 (13)
N2	0.0474 (8)	0.0476 (10)	0.0511 (9)	0.0017 (7)	0.0271 (7)	0.0071 (8)
N3	0.0486 (8)	0.0450 (10)	0.0495 (8)	−0.0003 (7)	0.0256 (7)	0.0014 (8)
C1	0.0449 (10)	0.0616 (14)	0.0504 (10)	−0.0010 (9)	0.0222 (8)	−0.0041 (11)
C2	0.0574 (11)	0.0548 (14)	0.0718 (13)	0.0049 (10)	0.0310 (10)	−0.0039 (12)
C3	0.0687 (13)	0.0503 (14)	0.0912 (14)	0.0033 (10)	0.0436 (12)	0.0046 (13)
C4	0.0591 (12)	0.0523 (14)	0.0727 (13)	−0.0005 (10)	0.0380 (10)	0.0022 (11)
C5	0.0407 (9)	0.0496 (12)	0.0464 (10)	0.0001 (8)	0.0171 (8)	−0.0023 (9)
C6	0.0515 (10)	0.0528 (13)	0.0532 (11)	−0.0004 (9)	0.0264 (8)	0.0018 (10)
C7	0.0591 (12)	0.0620 (15)	0.0681 (12)	0.0062 (10)	0.0345 (10)	−0.0010 (12)
C8	0.0482 (10)	0.0575 (14)	0.0555 (11)	0.0037 (9)	0.0227 (9)	0.0151 (11)
C9	0.0534 (11)	0.0523 (13)	0.0606 (12)	0.0079 (9)	0.0257 (9)	0.0132 (11)
C10	0.0420 (9)	0.0424 (11)	0.0408 (9)	0.0002 (8)	0.0141 (7)	−0.0007 (9)
C11	0.0414 (9)	0.0431 (11)	0.0420 (9)	−0.0018 (8)	0.0153 (7)	−0.0044 (9)
C12	0.0559 (11)	0.0524 (13)	0.0503 (10)	0.0055 (9)	0.0203 (9)	−0.0023 (10)
C13	0.0493 (11)	0.0630 (15)	0.0632 (12)	0.0073 (10)	0.0214 (10)	−0.0177 (12)
C14	0.0557 (12)	0.0697 (16)	0.0726 (14)	−0.0102 (10)	0.0366 (10)	−0.0184 (13)
C15	0.0710 (13)	0.0543 (14)	0.0783 (14)	−0.0056 (11)	0.0464 (11)	0.0027 (12)
C16	0.0563 (11)	0.0451 (12)	0.0658 (12)	0.0016 (9)	0.0319 (9)	0.0011 (10)

Geometric parameters (Å, º) top

O1—C8	1.2105 (19)	C8—C9	1.501 (2)
N1—C7	1.138 (2)	C9—H9A	0.9700
N2—N3	1.4096 (17)	C9—H9B	0.9700
N2—C5	1.417 (2)	C9—C10	1.479 (2)
N2—C8	1.377 (2)	C10—C11	1.468 (2)
N3—C10	1.289 (2)	C11—C12	1.384 (2)
C1—C2	1.374 (3)	C11—C16	1.379 (2)
C1—C6	1.382 (2)	C12—H12	0.9300
C1—C7	1.445 (2)	C12—C13	1.384 (2)
C2—H2	0.9300	C13—H13	0.9300
C2—C3	1.379 (2)	C13—C14	1.368 (3)
C3—H3	0.9300	C14—H14	0.9300
C3—C4	1.381 (2)	C14—C15	1.379 (3)
C4—H4	0.9300	C15—H15	0.9300
C4—C5	1.378 (2)	C15—C16	1.377 (2)
C5—C6	1.386 (2)	C16—H16	0.9300
C6—H6	0.9300

N3—N2—C5	118.46 (15)	C8—C9—H9B	111.3
C8—N2—N3	112.64 (13)	H9A—C9—H9B	109.2
C8—N2—C5	128.83 (14)	C10—C9—C8	102.19 (15)
C10—N3—N2	107.08 (14)	C10—C9—H9A	111.3
C2—C1—C6	121.59 (16)	C10—C9—H9B	111.3
C2—C1—C7	120.86 (18)	N3—C10—C9	113.07 (14)
C6—C1—C7	117.55 (19)	N3—C10—C11	121.66 (16)
C1—C2—H2	120.7	C11—C10—C9	125.27 (15)
C1—C2—C3	118.59 (18)	C12—C11—C10	120.09 (17)
C3—C2—H2	120.7	C16—C11—C10	121.17 (16)
C2—C3—H3	119.7	C16—C11—C12	118.73 (15)
C2—C3—C4	120.6 (2)	C11—C12—H12	119.8
C4—C3—H3	119.7	C13—C12—C11	120.39 (19)
C3—C4—H4	119.8	C13—C12—H12	119.8
C5—C4—C3	120.37 (17)	C12—C13—H13	119.9
C5—C4—H4	119.8	C14—C13—C12	120.24 (18)
C4—C5—N2	120.32 (15)	C14—C13—H13	119.9
C4—C5—C6	119.48 (17)	C13—C14—H14	120.1
C6—C5—N2	120.20 (17)	C13—C14—C15	119.82 (17)
C1—C6—C5	119.32 (19)	C15—C14—H14	120.1
C1—C6—H6	120.3	C14—C15—H15	120.0
C5—C6—H6	120.3	C16—C15—C14	119.97 (19)
N1—C7—C1	177.8 (2)	C16—C15—H15	120.0
O1—C8—N2	126.74 (17)	C11—C16—H16	119.6
O1—C8—C9	128.31 (18)	C15—C16—C11	120.84 (18)
N2—C8—C9	104.95 (14)	C15—C16—H16	119.6
C8—C9—H9A	111.3

C5—N2—N3—C10	177.95 (14)	C3—C4—C5—C6	1.4 (3)
C8—N2—N3—C10	0.94 (18)	N2—C5—C6—C1	179.60 (15)
N3—N2—C5—C4	−3.1 (2)	C4—C5—C6—C1	−1.0 (2)
N3—N2—C5—C6	176.29 (14)	O1—C8—C9—C10	−178.40 (19)
C8—N2—C5—C4	173.33 (17)	N2—C8—C9—C10	2.61 (18)
C8—N2—C5—C6	−7.3 (3)	C8—C9—C10—N3	−2.28 (19)
N3—N2—C8—O1	178.67 (18)	C8—C9—C10—C11	177.51 (15)
N3—N2—C8—C9	−2.32 (19)	N3—C10—C11—C12	169.70 (16)
C5—N2—C8—O1	2.0 (3)	N3—C10—C11—C16	−9.4 (2)
C5—N2—C8—C9	−178.95 (16)	C9—C10—C11—C12	−10.1 (3)
N2—N3—C10—C9	0.97 (18)	C9—C10—C11—C16	170.82 (16)
N2—N3—C10—C11	−178.83 (14)	C10—C11—C12—C13	−178.80 (16)
C6—C1—C2—C3	0.6 (3)	C16—C11—C12—C13	0.3 (3)
C7—C1—C2—C3	−178.93 (17)	C10—C11—C16—C15	179.29 (16)
C2—C1—C6—C5	0.0 (3)	C12—C11—C16—C15	0.2 (3)
C7—C1—C6—C5	179.54 (16)	C11—C12—C13—C14	−0.5 (3)
C1—C2—C3—C4	−0.2 (3)	C12—C13—C14—C15	0.1 (3)
C2—C3—C4—C5	−0.8 (3)	C13—C14—C15—C16	0.4 (3)
C3—C4—C5—N2	−179.18 (16)	C14—C15—C16—C11	−0.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N3	0.93	2.44	2.785 (2)	102
C6—H6···O1	0.93	2.24	2.880 (3)	125

Experimental details

Crystal data
Chemical formula	C₁₆H₁₁N₃O
M_r	261.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.6683 (3), 17.8013 (7), 9.7574 (4)
β (°)	106.506 (4)
V (Å³)	1277.05 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.34 × 0.30 × 0.28

Data collection
Diffractometer	Agilent Xcalibur diffractometer with an Eos CCD detector
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.967, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5145, 2608, 1686
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.119, 1.02
No. of reflections	2608
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.13

Computer programs: CrysAlis PRO (Agilent, 2011), OLEX2.solve (Bourhis et al., 2012), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

This work was supported by the Key Scientific Research Fund, Xihua University (Z0820504), the Open Research Fund of the Key Laboratory of Food Biotechnology, Xihua University (SZJJ2012–006) and the Innovation Postgraduate Fund, Xihua University (YCJJ201243)

References

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