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Acta Crystallogr Sect E Struct Rep Online. 2012 September 1; 68(Pt 9): o2634.
Published online 2012 August 4. doi:  10.1107/S1600536812033971
PMCID: PMC3435661

1-[3-(4-Fluoro­phen­yl)-5-phenyl-4,5-dihydro-1H-pyrazol-1-yl]ethanone

Abstract

In the title compound, C17H15FN2O, the pyrazoline ring adopts a flattened envelope conformation. The dihedral angle between the fluoro-substituted benzene ring and the phenyl ring is 69.20 (5)°. In the crystal, a pair of C—H(...)O hydrogen bonds link neighbouring mol­ecules, forming an inversion dimer. The crystal structure is further consolidated by C—H(...)π inter­actions and by a π–π inter­action with a centroid–centroid distance of 3.7379 (6) Å.

Related literature  

For related structures, see: Fun et al. (2010 [triangle], 2012a [triangle],b [triangle]); Samshuddin et al. (2011 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]). For ring conformations, see: Cremer & Pople (1975 [triangle]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-o2634-scheme1.jpg

Experimental  

Crystal data  

  • C17H15FN2O
  • M r = 282.31
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-68-o2634-efi1.jpg
  • a = 13.0973 (6) Å
  • b = 8.6104 (4) Å
  • c = 24.5948 (12) Å
  • V = 2773.6 (2) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 100 K
  • 0.34 × 0.33 × 0.09 mm

Data collection  

  • Bruker APEX DUO CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.969, T max = 0.991
  • 25040 measured reflections
  • 4069 independent reflections
  • 3442 reflections with I > 2σ(I)
  • R int = 0.029

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.113
  • S = 1.03
  • 4069 reflections
  • 191 parameters
  • H-atom parameters constrained
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812033971/is5177sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033971/is5177Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812033971/is5177Isup3.cml

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

Acknowledgments

HKF and CWO thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). CWO also thanks the Malaysian Government and USM for the award of the post of Research Officer under Research University Grant No. 1001/PFIZIK/811160. BN thanks the UGC for financial assistance through the SAP and BSR one-time grant for the purchase of chemicals.

supplementary crystallographic information

Comment

In continuation of our work on synthesis of pyrazoline derivatives (Fun et al., 2010; Samshuddin et al., 2011), the title compound is prepared and crystal structure is reported.

In the title compound (Fig. 1), the pyrazoline (N1/N2/C7–C9) ring adopts a flattened envelope conformation [pucker atom at C9 with deviation of 0.065 (1) Å] with puckering parameters Q = 0.1082 (10) Å and [var phi] = 79.4 (5)° (Cremer & Pople, 1975). The dihedral angle between fluoro-substituted benzene ring (C1–C6) and the phenyl ring (C10–C15) is 69.20 (5)°. The bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable with the related structures (Fun et al., 2012a,b).

In the crystal packing (Fig. 2), pairs of C8—H8A···O1 hydrogen bonds (Table 1) link the neighbouring molecules to form dimers. The crystal is further consolidated by C13—H13A···Cg1 and C1—H1A···Cg2 interactions (Table 1), involving the pyrazoline ring (N1/N2/C7–C9; Cg1) and the phenyl ring (C10–C15; Cg2), respectively. A weak π–π interaction is observed with Cg2···Cg2(1-x, 1-y, 1-z) = 3.7379 (6) Å.

Experimental

A mixture of (2E)-1-(4-fluorophenyl)-3-phenylprop-2-en-1-one (2.26 g, 0.01 mol) and hydrazine hydrate (0.48 ml, 0.01 mol) in 30 ml acetic acid was refluxed for 6 h. The reaction mixture was cooled and poured into 50 ml ice-cold water. The precipitate was collected by filtration and purified by recrystallization from ethanol. The single crystals were grown from toluene by slow evaporation method (m.p. 392–394 K).

Refinement

All H atoms were positioned geometrically (C—H = 0.95, 0.98, 0.99 and 1.00 Å) with Uiso(H) = 1.2 or 1.5Ueq(C). A rotating group model was applied to the methyl group. In the final refinement, one outlier (0 6 0) was omitted.

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
The crystal packing of the title compound, viewed along the a axis. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

Crystal data

C17H15FN2OF(000) = 1184
Mr = 282.31Dx = 1.352 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 8833 reflections
a = 13.0973 (6) Åθ = 3.0–30.1°
b = 8.6104 (4) ŵ = 0.10 mm1
c = 24.5948 (12) ÅT = 100 K
V = 2773.6 (2) Å3Plate, colourless
Z = 80.34 × 0.33 × 0.09 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer4069 independent reflections
Radiation source: fine-focus sealed tube3442 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
[var phi] and ω scansθmax = 30.1°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −14→18
Tmin = 0.969, Tmax = 0.991k = −9→12
25040 measured reflectionsl = −34→34

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0593P)2 + 0.9304P] where P = (Fo2 + 2Fc2)/3
4069 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = −0.24 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.
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)

xyzUiso*/Ueq
F10.82344 (6)−0.34824 (9)0.79260 (3)0.03354 (18)
O10.34443 (6)0.10960 (9)0.53136 (3)0.02267 (17)
N10.49592 (6)−0.01792 (10)0.64081 (4)0.01708 (17)
N20.46304 (6)0.06398 (10)0.59506 (3)0.01737 (17)
C10.76046 (8)−0.09765 (12)0.67970 (4)0.0202 (2)
H1A0.7939−0.03810.65250.024*
C20.81782 (8)−0.18030 (13)0.71746 (5)0.0246 (2)
H2A0.8903−0.17760.71650.029*
C30.76748 (9)−0.26591 (13)0.75618 (4)0.0242 (2)
C40.66219 (9)−0.27418 (13)0.75934 (4)0.0248 (2)
H4A0.6297−0.33470.78660.030*
C50.60547 (8)−0.19140 (13)0.72153 (4)0.0223 (2)
H5A0.5330−0.19560.72280.027*
C60.65372 (8)−0.10171 (11)0.68153 (4)0.01726 (19)
C70.59451 (7)−0.01827 (11)0.64033 (4)0.01611 (18)
C80.64134 (7)0.06184 (12)0.59202 (4)0.01745 (19)
H8A0.6751−0.01340.56750.021*
H8B0.69160.14130.60350.021*
C90.54760 (7)0.13688 (11)0.56463 (4)0.01575 (18)
H9A0.54440.10430.52560.019*
C100.54856 (7)0.31268 (11)0.56813 (4)0.01515 (18)
C110.49159 (7)0.39548 (12)0.60596 (4)0.0186 (2)
H11A0.44870.34200.63080.022*
C120.49747 (8)0.55759 (13)0.60740 (4)0.0222 (2)
H12A0.45900.61420.63350.027*
C130.55944 (8)0.63580 (12)0.57079 (4)0.0220 (2)
H13A0.56220.74600.57130.026*
C140.61750 (8)0.55344 (12)0.53337 (4)0.0197 (2)
H14A0.66050.60710.50860.024*
C150.61256 (7)0.39232 (12)0.53229 (4)0.01723 (19)
H15A0.65300.33590.50700.021*
C160.36726 (7)0.04583 (12)0.57425 (4)0.01743 (19)
C170.29434 (8)−0.05575 (13)0.60548 (5)0.0233 (2)
H17A0.2245−0.03670.59280.035*
H17B0.2991−0.03150.64430.035*
H17C0.3120−0.16510.59960.035*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.0370 (4)0.0359 (4)0.0277 (4)0.0095 (3)−0.0118 (3)0.0057 (3)
O10.0190 (4)0.0253 (4)0.0237 (4)−0.0001 (3)−0.0042 (3)0.0026 (3)
N10.0155 (4)0.0176 (4)0.0182 (4)0.0005 (3)−0.0008 (3)0.0014 (3)
N20.0127 (4)0.0187 (4)0.0207 (4)−0.0015 (3)−0.0006 (3)0.0044 (3)
C10.0177 (5)0.0205 (5)0.0225 (5)0.0007 (4)−0.0028 (4)−0.0006 (4)
C20.0196 (5)0.0268 (5)0.0273 (5)0.0032 (4)−0.0067 (4)−0.0010 (4)
C30.0298 (6)0.0226 (5)0.0202 (5)0.0072 (4)−0.0084 (4)−0.0021 (4)
C40.0293 (6)0.0262 (5)0.0190 (5)0.0050 (4)0.0012 (4)0.0022 (4)
C50.0196 (5)0.0262 (5)0.0210 (5)0.0035 (4)0.0018 (4)0.0021 (4)
C60.0165 (4)0.0177 (4)0.0176 (4)0.0024 (3)−0.0012 (3)−0.0024 (3)
C70.0149 (4)0.0153 (4)0.0180 (4)0.0007 (3)0.0005 (3)−0.0019 (3)
C80.0126 (4)0.0180 (4)0.0218 (5)0.0006 (3)0.0009 (3)0.0015 (3)
C90.0122 (4)0.0166 (4)0.0184 (4)−0.0010 (3)0.0008 (3)0.0009 (3)
C100.0123 (4)0.0170 (4)0.0161 (4)0.0002 (3)−0.0023 (3)0.0004 (3)
C110.0153 (4)0.0215 (5)0.0189 (4)0.0009 (3)0.0008 (3)0.0000 (4)
C120.0203 (5)0.0223 (5)0.0241 (5)0.0034 (4)−0.0008 (4)−0.0055 (4)
C130.0219 (5)0.0166 (4)0.0275 (5)−0.0005 (4)−0.0054 (4)−0.0019 (4)
C140.0160 (4)0.0203 (5)0.0230 (5)−0.0035 (4)−0.0028 (4)0.0029 (4)
C150.0144 (4)0.0196 (5)0.0177 (4)−0.0002 (3)−0.0003 (3)−0.0002 (3)
C160.0137 (4)0.0168 (4)0.0218 (4)0.0000 (3)−0.0003 (3)−0.0020 (3)
C170.0149 (4)0.0279 (5)0.0271 (5)−0.0053 (4)0.0001 (4)0.0016 (4)

Geometric parameters (Å, º)

F1—C31.3572 (12)C8—H8A0.9900
O1—C161.2261 (13)C8—H8B0.9900
N1—C71.2914 (13)C9—C101.5162 (13)
N1—N21.3959 (11)C9—H9A1.0000
N2—C161.3639 (12)C10—C111.3896 (13)
N2—C91.4767 (12)C10—C151.3963 (13)
C1—C21.3903 (14)C11—C121.3984 (15)
C1—C61.3991 (14)C11—H11A0.9500
C1—H1A0.9500C12—C131.3866 (15)
C2—C31.3729 (16)C12—H12A0.9500
C2—H2A0.9500C13—C141.3886 (15)
C3—C41.3831 (16)C13—H13A0.9500
C4—C51.3875 (15)C14—C151.3891 (14)
C4—H4A0.9500C14—H14A0.9500
C5—C61.4012 (14)C15—H15A0.9500
C5—H5A0.9500C16—C171.5058 (14)
C6—C71.4644 (13)C17—H17A0.9800
C7—C81.5045 (14)C17—H17B0.9800
C8—C91.5422 (13)C17—H17C0.9800
C7—N1—N2107.59 (8)N2—C9—C8101.40 (7)
C16—N2—N1121.90 (8)C10—C9—C8112.76 (8)
C16—N2—C9123.25 (8)N2—C9—H9A109.6
N1—N2—C9113.07 (8)C10—C9—H9A109.6
C2—C1—C6120.37 (10)C8—C9—H9A109.6
C2—C1—H1A119.8C11—C10—C15119.55 (9)
C6—C1—H1A119.8C11—C10—C9123.07 (9)
C3—C2—C1118.60 (10)C15—C10—C9117.35 (8)
C3—C2—H2A120.7C10—C11—C12119.96 (9)
C1—C2—H2A120.7C10—C11—H11A120.0
F1—C3—C2118.61 (10)C12—C11—H11A120.0
F1—C3—C4118.32 (10)C13—C12—C11120.04 (10)
C2—C3—C4123.06 (10)C13—C12—H12A120.0
C3—C4—C5118.02 (10)C11—C12—H12A120.0
C3—C4—H4A121.0C12—C13—C14120.19 (10)
C5—C4—H4A121.0C12—C13—H13A119.9
C4—C5—C6120.81 (10)C14—C13—H13A119.9
C4—C5—H5A119.6C13—C14—C15119.82 (10)
C6—C5—H5A119.6C13—C14—H14A120.1
C1—C6—C5119.14 (9)C15—C14—H14A120.1
C1—C6—C7119.65 (9)C14—C15—C10120.42 (9)
C5—C6—C7121.15 (9)C14—C15—H15A119.8
N1—C7—C6121.63 (9)C10—C15—H15A119.8
N1—C7—C8114.44 (9)O1—C16—N2119.73 (9)
C6—C7—C8123.74 (9)O1—C16—C17122.97 (9)
C7—C8—C9102.27 (8)N2—C16—C17117.29 (9)
C7—C8—H8A111.3C16—C17—H17A109.5
C9—C8—H8A111.3C16—C17—H17B109.5
C7—C8—H8B111.3H17A—C17—H17B109.5
C9—C8—H8B111.3C16—C17—H17C109.5
H8A—C8—H8B109.2H17A—C17—H17C109.5
N2—C9—C10113.69 (8)H17B—C17—H17C109.5
C7—N1—N2—C16159.15 (9)N1—N2—C9—C10−110.76 (9)
C7—N1—N2—C9−6.08 (11)C16—N2—C9—C8−154.47 (9)
C6—C1—C2—C30.25 (16)N1—N2—C9—C810.53 (10)
C1—C2—C3—F1179.15 (9)C7—C8—C9—N2−10.18 (9)
C1—C2—C3—C40.17 (17)C7—C8—C9—C10111.76 (9)
F1—C3—C4—C5−179.15 (10)N2—C9—C10—C1114.38 (13)
C2—C3—C4—C5−0.16 (17)C8—C9—C10—C11−100.34 (10)
C3—C4—C5—C6−0.26 (16)N2—C9—C10—C15−167.56 (8)
C2—C1—C6—C5−0.66 (15)C8—C9—C10—C1577.72 (11)
C2—C1—C6—C7−177.92 (9)C15—C10—C11—C120.96 (14)
C4—C5—C6—C10.67 (16)C9—C10—C11—C12178.98 (9)
C4—C5—C6—C7177.89 (10)C10—C11—C12—C130.55 (15)
N2—N1—C7—C6−176.87 (8)C11—C12—C13—C14−1.38 (16)
N2—N1—C7—C8−1.65 (11)C12—C13—C14—C150.69 (15)
C1—C6—C7—N1−179.40 (9)C13—C14—C15—C100.84 (15)
C5—C6—C7—N13.40 (15)C11—C10—C15—C14−1.66 (14)
C1—C6—C7—C85.84 (15)C9—C10—C15—C14−179.79 (9)
C5—C6—C7—C8−171.37 (9)N1—N2—C16—O1−173.68 (9)
N1—C7—C8—C98.00 (11)C9—N2—C16—O1−9.96 (15)
C6—C7—C8—C9−176.89 (9)N1—N2—C16—C175.37 (14)
C16—N2—C9—C1084.23 (11)C9—N2—C16—C17169.09 (9)

Hydrogen-bond geometry (Å, º)

Cg1 and Cg2 are the centroids of the pyrazole N1/N2/C7–C9 ring and the phenyl C10–C15 ring, respectively.

D—H···AD—HH···AD···AD—H···A
C8—H8A···O1i0.992.583.3797 (13)138
C1—H1A···Cg2ii0.952.853.6856 (11)148
C13—H13A···Cg1iii0.952.733.6370 (11)161

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1, −y−3/2, z−1/2; (iii) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS5177).

References

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  • Bruker (2009). SADABS, APEX2 and SAINTBruker AXS Inc., Madison, Wisconsin, USA.
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.
  • Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.
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  • Fun, H.-K., Loh, W.-S., Sapnakumari, M., Narayana, B. & Sarojini, B. K. (2012b). Acta Cryst. E68, o2655–o2656. [PMC free article] [PubMed]
  • Samshuddin, S., Narayana, B., Baktir, Z., Akkurt, M. & Yathirajan, H. S. (2011). Der Pharma Chem. 3, 487–493.
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  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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