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Acta Cryst. (2008). E64, o1886    [ doi:10.1107/S1600536808026706 ]

5-(3-Fluorophenyl)-1-phenylpyrazolidin-3-one

Y.-Y. Liu, H. Shi, Q.-Y. Chu and H.-J. Zhu

Abstract top

In the molecule of the title compound, C15H13FN2O, the phenyl and fluorophenyl rings are oriented at a dihedral angle of 77.92 (3)°. The pyrazolidine ring adopts an envelope conformation. An intramolecular C-H...N hydrogen bond results in the formation of a five-membered ring adopting an envelope conformation. In the crystal structure, intermolecular N-H...O and C-H...O hydrogen bonds link the molecules. There are C-H...[pi] contacts between between aromatic H atoms and the phenyl and fluorophenyl rings. A [pi]-[pi] contact between phenyl rings [centroid-centroid distance = 3.926 (1) Å] is also observed.

Comment top

Pyrazolidin-3-one and its derivatives used as medicines and herbicides (Chiara & Garcia, 2005) have been developed most quickly, such as anodyne and antipyretic. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6) and C (C10-C15) are, of course, planar, and they are oriented at a dihedral angle of A/C = 77.92 (3)°. Ring B (N1/N2/C7-C9) adopts envelope conformation, with C8 atom displaced by 0.277 (3) Å from the plane of the other ring atoms. The intra- molecular C-H···N hydrogen bond (Table 1) results in the formation of a five-membered ring D (N1/C4/C5/C7/H4A) adopting envelope conformation, with N1 atom displaced by -0.326 (3) Å from the plane of the other ring atoms.

In the crystal structure, intermolecular N-H···O and C-H···O hydrogen bonds link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure. The C—H···π contacts (Table 1) between the phenyl rings and the aromatic H atoms and a π—π contact between phenyl rings Cg2···Cg2i [symmetry code: (i) -x, 1 - y, 1 - z, where Cg2 is centroid of the ring A (C1-C6)] further stabilize the structure, with centroid-centroid distance of 3.926 (1) Å.

Related literature top

For general background, see: Chiara & Garcia (2005). For related literature, see: Jia et al. (2008). For bond-length data, see: Allen et al. (1987). Cg2 is the centroid of the C1–C6 ring and Cg3 is the centroid of the C10–C15 ring.

Experimental top

The title compound was prepared according to the literature method (Jia et al., 2008). The crystals were obtained by dissolving the title compound (1.5 g) in ethyl acetate (25 ml) and evaporating the solvent slowly at room temperature for about 10 d.

Refinement top

H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.93, 0.98 and 0.97 Å for aromatic, methine and methylene H, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bond is shown as dashed line.
[Figure 2] Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
5-(3-fluorophenyl)-1-phenylpyrazolidin-3-one top
Crystal data top
C15H13FN2OF(000) = 536
Mr = 256.27Dx = 1.273 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 10.265 (2) Åθ = 9–12°
b = 7.3130 (15) ŵ = 0.09 mm−1
c = 17.822 (4) ÅT = 294 K
β = 92.39 (3)°Needle, colorless
V = 1336.7 (5) Å30.30 × 0.20 × 0.10 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		1231 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.000
graphiteθmax = 25.2°, θmin = 2.0°
ω/2θ scansh = −12→12
Absorption correction: ψ scan
(North et al., 1968)		k = 0→8
Tmin = 0.973, Tmax = 0.991l = 0→21
2393 measured reflections3 standard reflections every 120 min
2393 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.081H-atom parameters constrained
wR(F2) = 0.232 w = 1/[σ2(Fo2) + (0.1065P)2 + 0.1962P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
2393 reflectionsΔρmax = 0.34 e Å−3
166 parametersΔρmin = −0.75 e Å−3
Primary atom site location: structure-invariant direct methods
Crystal data top
C15H13FN2OV = 1336.7 (5) Å3
Mr = 256.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.265 (2) ŵ = 0.09 mm−1
b = 7.3130 (15) ÅT = 294 K
c = 17.822 (4) Å0.30 × 0.20 × 0.10 mm
β = 92.39 (3)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1231 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.000
Tmin = 0.973, Tmax = 0.991θmax = 25.2°
2393 measured reflections3 standard reflections every 120 min
2393 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.081H-atom parameters constrained
wR(F2) = 0.232Δρmax = 0.34 e Å−3
S = 1.07Δρmin = −0.75 e Å−3
2393 reflectionsAbsolute structure: ?
166 parametersFlack parameter: ?
? restraintsRogers parameter: ?
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 > 2sigma(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
xyzUiso*/Ueq
O0.0023 (3)0.2565 (4)0.22989 (17)0.0567 (8)
F0.2688 (3)0.7468 (5)0.56248 (19)0.098
N10.2364 (3)0.0858 (4)0.35618 (19)0.0407 (8)
C10.2186 (8)0.5785 (10)0.5378 (4)0.104 (2)
N20.1332 (3)0.0777 (4)0.3021 (2)0.0477 (9)
H2A0.0965−0.02350.28860.057*
C20.1419 (7)0.4819 (12)0.5800 (4)0.095 (2)
H2B0.11740.52520.62640.114*
C30.0997 (6)0.3176 (11)0.5537 (3)0.0873 (18)
H3A0.04260.24920.58160.105*
C40.1399 (5)0.2505 (7)0.4868 (3)0.0650 (13)
H4A0.11120.13610.47040.078*
C50.2215 (4)0.3492 (6)0.4436 (2)0.0488 (11)
C60.2666 (6)0.5199 (7)0.4691 (3)0.0790 (16)
H6A0.32450.58980.44240.095*
C70.2639 (4)0.2853 (5)0.3683 (2)0.0421 (10)
H7A0.35760.30730.36470.051*
C80.1895 (4)0.3791 (5)0.3012 (2)0.0452 (10)
H8A0.14350.48700.31740.054*
H8B0.24870.41370.26260.054*
C90.0967 (4)0.2358 (5)0.2735 (2)0.0433 (10)
C100.3413 (3)−0.0333 (5)0.3443 (2)0.0385 (9)
C110.4505 (4)−0.0252 (6)0.3943 (2)0.0509 (11)
H11A0.45290.06110.43270.061*
C120.5555 (4)−0.1441 (7)0.3875 (3)0.0592 (13)
H12A0.6282−0.13590.42030.071*
C130.5499 (5)−0.2750 (6)0.3310 (3)0.0660 (14)
H13A0.6185−0.35690.32650.079*
C140.4453 (4)−0.2840 (6)0.2825 (3)0.0573 (12)
H14A0.4430−0.37180.24470.069*
C150.3405 (4)−0.1633 (5)0.2880 (2)0.0423 (10)
H15A0.2699−0.17060.25370.051*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O0.0586 (18)0.0318 (16)0.079 (2)0.0078 (14)−0.0066 (17)0.0028 (15)
F0.0980.0980.0980.0000.0040.000
N10.0375 (18)0.0253 (17)0.059 (2)0.0030 (14)−0.0036 (16)−0.0029 (15)
C10.125 (6)0.083 (5)0.101 (5)0.018 (4)−0.022 (5)−0.058 (4)
N20.0402 (19)0.0242 (17)0.078 (3)0.0014 (15)−0.0117 (18)0.0065 (16)
C20.089 (5)0.132 (7)0.063 (4)0.044 (5)0.007 (3)−0.022 (4)
C30.081 (4)0.117 (6)0.064 (4)0.015 (4)0.002 (3)0.008 (4)
C40.055 (3)0.067 (3)0.072 (3)0.008 (3)−0.002 (3)0.000 (3)
C50.043 (2)0.045 (3)0.058 (3)0.010 (2)−0.004 (2)−0.005 (2)
C60.109 (4)0.063 (3)0.065 (3)−0.010 (3)0.006 (3)−0.027 (3)
C70.040 (2)0.0212 (19)0.066 (3)−0.0020 (17)0.0037 (19)−0.0048 (19)
C80.040 (2)0.030 (2)0.066 (3)−0.0010 (18)0.007 (2)−0.003 (2)
C90.042 (2)0.031 (2)0.057 (2)0.0024 (19)0.005 (2)−0.013 (2)
C100.032 (2)0.031 (2)0.052 (2)0.0004 (17)−0.0015 (18)0.0085 (19)
C110.047 (2)0.049 (3)0.056 (3)0.014 (2)−0.004 (2)−0.009 (2)
C120.051 (3)0.063 (3)0.062 (3)0.006 (2)−0.017 (2)0.009 (3)
C130.052 (3)0.043 (3)0.105 (4)0.012 (2)0.023 (3)0.001 (3)
C140.055 (3)0.042 (3)0.076 (3)0.006 (2)0.024 (2)−0.017 (2)
C150.038 (2)0.039 (2)0.050 (2)−0.0045 (19)0.0006 (18)−0.0047 (19)
Geometric parameters (Å, °) top
O—C91.226 (5)C6—H6A0.9300
F—C11.398 (7)C7—C81.552 (6)
N1—N21.404 (4)C7—H7A0.9800
N1—C101.408 (5)C8—C91.487 (5)
N1—C71.500 (4)C8—H8A0.9700
C1—C21.317 (9)C8—H8B0.9700
C1—C61.405 (9)C10—C151.381 (5)
N2—C91.311 (5)C10—C111.404 (5)
N2—H2A0.8600C11—C121.394 (6)
C2—C31.354 (9)C11—H11A0.9300
C2—H2B0.9300C12—C131.389 (6)
C3—C41.370 (8)C12—H12A0.9300
C3—H3A0.9300C13—C141.353 (6)
C4—C51.366 (7)C13—H13A0.9300
C4—H4A0.9300C14—C151.398 (6)
C5—C61.400 (6)C14—H14A0.9300
C5—C71.502 (6)C15—H15A0.9300
N2—N1—C10115.5 (3)C8—C7—H7A109.2
N2—N1—C7105.8 (3)C9—C8—C7103.4 (3)
C10—N1—C7118.9 (3)C9—C8—H8A111.1
C2—C1—F120.9 (7)C7—C8—H8A111.1
C2—C1—C6125.0 (6)C9—C8—H8B111.1
F—C1—C6113.9 (7)C7—C8—H8B111.1
C9—N2—N1115.1 (3)H8A—C8—H8B109.0
C9—N2—H2A122.4O—C9—N2124.1 (4)
N1—N2—H2A122.4O—C9—C8127.0 (4)
C1—C2—C3117.9 (6)N2—C9—C8108.9 (3)
C1—C2—H2B121.0C15—C10—C11118.0 (4)
C3—C2—H2B121.0C15—C10—N1123.6 (3)
C2—C3—C4121.1 (6)C11—C10—N1118.3 (3)
C2—C3—H3A119.5C12—C11—C10121.2 (4)
C4—C3—H3A119.5C12—C11—H11A119.4
C5—C4—C3121.0 (5)C10—C11—H11A119.4
C5—C4—H4A119.5C13—C12—C11119.0 (4)
C3—C4—H4A119.5C13—C12—H12A120.5
C4—C5—C6119.4 (4)C11—C12—H12A120.5
C4—C5—C7123.0 (4)C14—C13—C12120.3 (4)
C6—C5—C7117.6 (4)C14—C13—H13A119.8
C5—C6—C1115.6 (6)C12—C13—H13A119.8
C5—C6—H6A122.2C13—C14—C15121.1 (4)
C1—C6—H6A122.2C13—C14—H14A119.4
N1—C7—C5111.8 (3)C15—C14—H14A119.4
N1—C7—C8103.6 (3)C10—C15—C14120.3 (4)
C5—C7—C8113.6 (3)C10—C15—H15A119.8
N1—C7—H7A109.2C14—C15—H15A119.8
C5—C7—H7A109.2
C10—N1—N2—C9−128.7 (4)C6—C5—C7—C8−76.9 (5)
C7—N1—N2—C95.0 (5)N1—C7—C8—C917.4 (4)
F—C1—C2—C3−178.1 (5)C5—C7—C8—C9−104.2 (4)
C6—C1—C2—C3−3.9 (11)N1—N2—C9—O−174.3 (4)
C1—C2—C3—C42.6 (9)N1—N2—C9—C87.0 (5)
C2—C3—C4—C5−1.4 (8)C7—C8—C9—O166.0 (4)
C3—C4—C5—C61.2 (7)C7—C8—C9—N2−15.3 (4)
C3—C4—C5—C7−177.3 (4)N2—N1—C10—C15−6.1 (5)
C4—C5—C6—C1−2.1 (7)C7—N1—C10—C15−133.5 (4)
C7—C5—C6—C1176.5 (5)N2—N1—C10—C11176.8 (3)
C2—C1—C6—C53.6 (10)C7—N1—C10—C1149.4 (5)
F—C1—C6—C5178.2 (5)C15—C10—C11—C120.2 (6)
N2—N1—C7—C5108.7 (3)N1—C10—C11—C12177.4 (4)
C10—N1—C7—C5−119.4 (4)C10—C11—C12—C13−1.3 (7)
N2—N1—C7—C8−13.9 (4)C11—C12—C13—C141.4 (7)
C10—N1—C7—C8117.9 (4)C12—C13—C14—C15−0.4 (7)
C4—C5—C7—N1−15.1 (5)C11—C10—C15—C140.8 (6)
C6—C5—C7—N1166.3 (4)N1—C10—C15—C14−176.2 (4)
C4—C5—C7—C8101.7 (4)C13—C14—C15—C10−0.8 (7)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Oi0.861.922.777 (4)172.
C4—H4A···N10.932.482.836 (6)103.
C8—H8A···Oii0.972.593.422 (5)143.
C6—H6A···Cg3iii0.932.963.866 (3)165.
C12—H12A···Cg2iv0.933.053.751 (3)134.
C14—H14A···Cg3v0.932.803.654 (3)153.
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) x, y+1, z; (iv) −x+1, −y, −z+1; (v) −x+1, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Oi0.861.922.777 (4)172.
C4—H4A···N10.932.482.836 (6)103.
C8—H8A···Oii0.972.593.422 (5)143.
C6—H6A···Cg3iii0.932.963.866 (3)165.
C12—H12A···Cg2iv0.933.053.751 (3)134.
C14—H14A···Cg3v0.932.803.654 (3)153.
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, y+1/2, −z+1/2; (iii) x, y+1, z; (iv) −x+1, −y, −z+1; (v) −x+1, y−1/2, −z+1/2.
Acknowledgements top

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

references
References top

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Jia, H.-S., Li, Y.-F., Liu, Y.-Y., Liu, S. & Zhu, H.-J. (2008). Acta Cryst. E64, o855.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.