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

Abstract

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,

• a = 7.6683 (3) Å

• b = 17.8013 (7) Å

• c = 9.7574 (4) Å

• β = 106.506 (4)°

• V = 1277.05 (9) ų

• 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[F ² > 2σ(F ²)] = 0.048

• wR(F ²) = 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812027444/zs2212Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

H atoms were positioned geometrically (C—H = 0.95–0.98 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

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

Crystal data

C16H11N3O	F(000) = 544
Mr = 261.28	Dx = 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

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	Rint = 0.023
Detector resolution: 16.0874 pixels mm-1	θmax = 26.4°, θmin = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −10→22
Tmin = 0.967, Tmax = 1.000	l = −12→11
5145 measured reflections

Refinement

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(Fo2) + (0.0461P)2 + 0.0009P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2608 reflections	Δρmax = 0.14 e Å−3
182 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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