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Acta Crystallogr Sect E Struct Rep Online. 2012 September 1; 68(Pt 9): o2655–o2656.
Published online 2012 August 8. doi:  10.1107/S1600536812034368
PMCID: PMC3435682

1-[5-(4-Bromo­phen­yl)-3-(4-fluoro­phen­yl)-4,5-dihydro-1H-pyrazol-1-yl]butan-1-one

Abstract

In the title compound, C19H18BrFN2O, the benzene rings form dihedral angles of 5.38 (7) and 85.48 (7)° with the mean plane of the 4,5-dihydro-1H-pyrazole ring (r.m.s. deviation = 0.0849 Å), which approximates to an envelope conformation with the –CH2– group as the flap. The dihedral angle between the benzene rings is 82.86 (7)°. In the crystal, C—H(...)F and C—H(...)O hydrogen bonds link the mol­ecules to form inversion dimers and together these generate chains along [011]. The crystal packing also features C—H(...)π inter­actions.

Related literature  

For background to pyrazoline derivatives, see: Fun et al. (2010 [triangle]); Samshuddin et al. (2011 [triangle]). For related structures, see: Fun, Quah et al. (2012 [triangle]); Fun, Loh et al. (2012 [triangle]). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-68-o2655-scheme1.jpg

Experimental  

Crystal data  

  • C19H18BrFN2O
  • M r = 389.26
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o2655-efi1.jpg
  • a = 6.7502 (3) Å
  • b = 10.1253 (5) Å
  • c = 13.7792 (8) Å
  • α = 105.354 (1)°
  • β = 98.976 (1)°
  • γ = 107.369 (1)°
  • V = 838.01 (7) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.47 mm−1
  • T = 100 K
  • 0.28 × 0.23 × 0.08 mm

Data collection  

  • Bruker SMART APEXII DUO CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.546, T max = 0.823
  • 17838 measured reflections
  • 4816 independent reflections
  • 4458 reflections with I > 2σ(I)
  • R int = 0.023

Refinement  

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.066
  • S = 1.06
  • 4816 reflections
  • 218 parameters
  • H-atom parameters constrained
  • Δρmax = 0.49 e Å−3
  • Δρmin = −0.63 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/S1600536812034368/hb6918sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812034368/hb6918Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812034368/hb6918Isup3.cml

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

Acknowledgments

HKF and WSL thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160). WSL also thanks the Malaysian government and USM for the post of Research Officer under the Research University Grant (No. 1001/PFIZIK/811160). BN thanks the UGC for financial assistance through 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 its crystal structure is reported.

In the title compound, Fig. 1, the benzene rings (C1–C6 & C10–C15) form dihedral angles of 5.38 (7) and 85.48 (7)°, respectively, with the mean plane of 4,5-dihydro-1H-pyrazole ring (N1/N2/C7–C9, r.m.s. deviation = 0.0849 Å). The dihedral angle between the two benzene rings is 82.86 (7) °. Bond lengths and angles are comparable with those in related structures (Fun, Quah et al., 2012; Fun, Loh et al., 2012).

In the crystal packing as shown in Fig. 2, C11—H11A···F1 and C14—H14A···O1 hydrogen bonds (Table 1) link the molecules to form dimers, generating chains along the [011]. The crystal packing is further consolidated by C17—H17B···Cg1 and C5—H5A···Cg2 (Table 1) interactions, where Cg1 and Cg2 are the centroids of C1–C5 and C10–C15 benzene rings, respectively.

Experimental

A mixture of (2E)-3-(4-bromophenyl)-1-(4-fluorophenyl)prop-2-en-1-one (3.05 g, 0.01 mol) and hydrazine hydrate (0.48 ml, 0.01 mol) in 30 ml butyric 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. Colourless plates were grown from acetone solution by slow evaporation method. M. p.: 383–385 K.

Refinement

All the H atoms were located geometrically and were refined using a riding model with Uiso(H) = 1.2 or 1.5 Ueq(C) [C–H = 0.95 to 0.99 Å]. A rotating group model was applied to the methyl group. In the final refinement, eighteen outliners were omitted, 3 - 3 7, 0 - 3 10, 4 0 3, 2 - 4 9, 2 0 2, 4 - 1 4, 1 0 0, -2 4 6, 2 5 1, -1 2 4, 1 0 5, -2 2 6, -2 5 4, 0 6 3, -1 - 1 8, 1 - 3 9, 15 2 and 1 2 1.

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids.
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

C19H18BrFN2OZ = 2
Mr = 389.26F(000) = 396
Triclinic, P1Dx = 1.543 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7502 (3) ÅCell parameters from 9994 reflections
b = 10.1253 (5) Åθ = 3.1–33.0°
c = 13.7792 (8) ŵ = 2.47 mm1
α = 105.354 (1)°T = 100 K
β = 98.976 (1)°Plate, colourless
γ = 107.369 (1)°0.28 × 0.23 × 0.08 mm
V = 838.01 (7) Å3

Data collection

Bruker SMART APEXII DUO CCD diffractometer4816 independent reflections
Radiation source: fine-focus sealed tube4458 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
[var phi] and ω scansθmax = 30.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −9→9
Tmin = 0.546, Tmax = 0.823k = −14→14
17838 measured reflectionsl = −19→19

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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 1.06w = 1/[σ2(Fo2) + (0.0342P)2 + 0.3618P] where P = (Fo2 + 2Fc2)/3
4816 reflections(Δ/σ)max = 0.001
218 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = −0.63 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
Br10.29346 (2)1.105034 (15)0.629792 (11)0.02435 (5)
F11.22640 (16)0.30984 (10)0.49188 (7)0.02653 (19)
O10.44837 (15)0.73712 (10)0.95847 (7)0.01715 (18)
N10.69619 (17)0.56573 (11)0.78382 (8)0.01292 (18)
N20.65164 (17)0.67234 (11)0.85431 (8)0.01310 (19)
C10.8653 (2)0.39253 (14)0.64641 (10)0.0171 (2)
H1A0.73510.34380.66080.020*
C20.9522 (2)0.31297 (15)0.57824 (11)0.0201 (2)
H2A0.88340.21000.54570.024*
C31.1414 (2)0.38745 (16)0.55897 (10)0.0184 (2)
C41.2486 (2)0.53618 (15)0.60412 (10)0.0175 (2)
H4A1.37880.58360.58920.021*
C51.1603 (2)0.61528 (14)0.67260 (10)0.0150 (2)
H5A1.23100.71820.70490.018*
C60.96862 (19)0.54438 (13)0.69403 (9)0.0133 (2)
C70.87764 (19)0.62814 (13)0.76656 (9)0.0127 (2)
C80.98525 (19)0.78883 (13)0.83134 (10)0.0149 (2)
H8A1.03760.84930.78830.018*
H8B1.10650.80460.88910.018*
C90.80040 (19)0.82300 (13)0.87232 (9)0.0131 (2)
H9A0.85110.88010.94840.016*
C100.68978 (19)0.89988 (13)0.81387 (9)0.0129 (2)
C110.6768 (2)0.87756 (14)0.70818 (10)0.0165 (2)
H11A0.74820.81920.67350.020*
C120.5613 (2)0.93907 (14)0.65294 (10)0.0183 (2)
H12A0.55270.92290.58100.022*
C130.4586 (2)1.02469 (14)0.70504 (10)0.0167 (2)
C140.4748 (2)1.05360 (13)0.81074 (10)0.0158 (2)
H14A0.40841.11550.84580.019*
C150.59010 (19)0.99012 (13)0.86442 (9)0.0143 (2)
H15A0.60121.00850.93670.017*
C160.48284 (19)0.63837 (13)0.89729 (9)0.0128 (2)
C170.34922 (19)0.47749 (13)0.86741 (9)0.0137 (2)
H17A0.44230.42490.88770.016*
H17B0.29120.43630.79090.016*
C180.1640 (2)0.45162 (14)0.91894 (10)0.0157 (2)
H18A0.06740.50070.89650.019*
H18B0.22130.49590.99540.019*
C190.0363 (2)0.28890 (16)0.89136 (11)0.0226 (3)
H19A−0.07780.27650.92790.034*
H19B0.13210.23960.91230.034*
H19C−0.02740.24590.81610.034*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.02830 (8)0.02231 (8)0.02494 (8)0.01276 (6)0.00379 (5)0.00926 (5)
F10.0359 (5)0.0316 (5)0.0200 (4)0.0222 (4)0.0148 (4)0.0051 (3)
O10.0176 (4)0.0163 (4)0.0177 (4)0.0058 (3)0.0095 (3)0.0033 (3)
N10.0128 (4)0.0133 (4)0.0136 (4)0.0056 (4)0.0056 (4)0.0037 (4)
N20.0127 (4)0.0109 (4)0.0156 (5)0.0035 (4)0.0068 (4)0.0030 (4)
C10.0156 (5)0.0162 (5)0.0185 (6)0.0053 (4)0.0053 (5)0.0042 (5)
C20.0235 (6)0.0180 (6)0.0174 (6)0.0097 (5)0.0041 (5)0.0018 (5)
C30.0242 (6)0.0247 (6)0.0122 (5)0.0163 (5)0.0071 (5)0.0054 (5)
C40.0169 (6)0.0244 (6)0.0167 (5)0.0108 (5)0.0085 (5)0.0092 (5)
C50.0142 (5)0.0174 (5)0.0153 (5)0.0070 (4)0.0058 (4)0.0058 (4)
C60.0128 (5)0.0162 (5)0.0123 (5)0.0069 (4)0.0041 (4)0.0047 (4)
C70.0110 (5)0.0134 (5)0.0137 (5)0.0047 (4)0.0036 (4)0.0040 (4)
C80.0110 (5)0.0142 (5)0.0187 (5)0.0032 (4)0.0066 (4)0.0037 (4)
C90.0117 (5)0.0120 (5)0.0147 (5)0.0026 (4)0.0059 (4)0.0032 (4)
C100.0126 (5)0.0115 (5)0.0134 (5)0.0027 (4)0.0057 (4)0.0027 (4)
C110.0190 (6)0.0170 (5)0.0154 (5)0.0077 (5)0.0096 (5)0.0041 (4)
C120.0224 (6)0.0186 (6)0.0151 (5)0.0072 (5)0.0083 (5)0.0054 (5)
C130.0168 (5)0.0142 (5)0.0194 (6)0.0050 (4)0.0054 (5)0.0063 (4)
C140.0151 (5)0.0131 (5)0.0193 (6)0.0046 (4)0.0078 (4)0.0036 (4)
C150.0145 (5)0.0132 (5)0.0142 (5)0.0034 (4)0.0072 (4)0.0026 (4)
C160.0113 (5)0.0154 (5)0.0124 (5)0.0046 (4)0.0041 (4)0.0052 (4)
C170.0123 (5)0.0140 (5)0.0146 (5)0.0035 (4)0.0048 (4)0.0048 (4)
C180.0127 (5)0.0191 (5)0.0165 (5)0.0039 (4)0.0063 (4)0.0080 (4)
C190.0180 (6)0.0216 (6)0.0240 (7)−0.0006 (5)0.0067 (5)0.0087 (5)

Geometric parameters (Å, º)

Br1—C131.8991 (13)C9—C101.5177 (17)
F1—C31.3606 (14)C9—H9A1.0000
O1—C161.2322 (15)C10—C151.3960 (16)
N1—C71.2901 (16)C10—C111.3978 (17)
N1—N21.3888 (13)C11—C121.3894 (19)
N2—C161.3608 (15)C11—H11A0.9500
N2—C91.4846 (15)C12—C131.3902 (17)
C1—C21.3891 (17)C12—H12A0.9500
C1—C61.4013 (17)C13—C141.3872 (18)
C1—H1A0.9500C14—C151.3918 (18)
C2—C31.381 (2)C14—H14A0.9500
C2—H2A0.9500C15—H15A0.9500
C3—C41.375 (2)C16—C171.5127 (17)
C4—C51.3957 (16)C17—C181.5219 (16)
C4—H4A0.9500C17—H17A0.9900
C5—C61.3975 (17)C17—H17B0.9900
C5—H5A0.9500C18—C191.5232 (19)
C6—C71.4660 (16)C18—H18A0.9900
C7—C81.5148 (17)C18—H18B0.9900
C8—C91.5394 (16)C19—H19A0.9800
C8—H8A0.9900C19—H19B0.9800
C8—H8B0.9900C19—H19C0.9800
C7—N1—N2107.76 (10)C15—C10—C9120.04 (11)
C16—N2—N1122.03 (10)C11—C10—C9121.35 (10)
C16—N2—C9125.22 (10)C12—C11—C10121.24 (11)
N1—N2—C9112.69 (9)C12—C11—H11A119.4
C2—C1—C6120.32 (12)C10—C11—H11A119.4
C2—C1—H1A119.8C11—C12—C13118.64 (12)
C6—C1—H1A119.8C11—C12—H12A120.7
C3—C2—C1118.28 (12)C13—C12—H12A120.7
C3—C2—H2A120.9C14—C13—C12121.63 (12)
C1—C2—H2A120.9C14—C13—Br1119.20 (9)
F1—C3—C4118.22 (12)C12—C13—Br1119.17 (10)
F1—C3—C2118.38 (12)C13—C14—C15118.73 (11)
C4—C3—C2123.40 (12)C13—C14—H14A120.6
C3—C4—C5117.96 (12)C15—C14—H14A120.6
C3—C4—H4A121.0C14—C15—C10121.14 (11)
C5—C4—H4A121.0C14—C15—H15A119.4
C4—C5—C6120.54 (12)C10—C15—H15A119.4
C4—C5—H5A119.7O1—C16—N2119.59 (11)
C6—C5—H5A119.7O1—C16—C17123.68 (11)
C5—C6—C1119.50 (11)N2—C16—C17116.72 (10)
C5—C6—C7120.20 (11)C16—C17—C18112.50 (10)
C1—C6—C7120.30 (11)C16—C17—H17A109.1
N1—C7—C6121.06 (11)C18—C17—H17A109.1
N1—C7—C8113.62 (10)C16—C17—H17B109.1
C6—C7—C8125.25 (10)C18—C17—H17B109.1
C7—C8—C9101.79 (9)H17A—C17—H17B107.8
C7—C8—H8A111.4C17—C18—C19111.82 (11)
C9—C8—H8A111.4C17—C18—H18A109.3
C7—C8—H8B111.4C19—C18—H18A109.3
C9—C8—H8B111.4C17—C18—H18B109.3
H8A—C8—H8B109.3C19—C18—H18B109.3
N2—C9—C10110.08 (10)H18A—C18—H18B107.9
N2—C9—C8100.37 (9)C18—C19—H19A109.5
C10—C9—C8114.80 (10)C18—C19—H19B109.5
N2—C9—H9A110.4H19A—C19—H19B109.5
C10—C9—H9A110.4C18—C19—H19C109.5
C8—C9—H9A110.4H19A—C19—H19C109.5
C15—C10—C11118.55 (11)H19B—C19—H19C109.5
C7—N1—N2—C16−172.51 (11)C7—C8—C9—N217.81 (11)
C7—N1—N2—C910.01 (13)C7—C8—C9—C10−100.16 (11)
C6—C1—C2—C3−0.1 (2)N2—C9—C10—C1594.86 (13)
C1—C2—C3—F1−179.72 (12)C8—C9—C10—C15−152.80 (11)
C1—C2—C3—C40.3 (2)N2—C9—C10—C11−82.31 (14)
F1—C3—C4—C5179.79 (11)C8—C9—C10—C1130.03 (16)
C2—C3—C4—C5−0.2 (2)C15—C10—C11—C12−2.23 (19)
C3—C4—C5—C6−0.02 (19)C9—C10—C11—C12174.98 (12)
C4—C5—C6—C10.20 (19)C10—C11—C12—C130.3 (2)
C4—C5—C6—C7179.61 (11)C11—C12—C13—C142.1 (2)
C2—C1—C6—C5−0.13 (19)C11—C12—C13—Br1−178.25 (10)
C2—C1—C6—C7−179.54 (12)C12—C13—C14—C15−2.6 (2)
N2—N1—C7—C6−179.32 (10)Br1—C13—C14—C15177.84 (9)
N2—N1—C7—C83.50 (14)C13—C14—C15—C100.53 (19)
C5—C6—C7—N1176.94 (12)C11—C10—C15—C141.81 (18)
C1—C6—C7—N1−3.66 (18)C9—C10—C15—C14−175.44 (11)
C5—C6—C7—C8−6.23 (18)N1—N2—C16—O1−179.08 (11)
C1—C6—C7—C8173.18 (12)C9—N2—C16—O1−1.92 (18)
N1—C7—C8—C9−14.48 (14)N1—N2—C16—C172.02 (16)
C6—C7—C8—C9168.48 (11)C9—N2—C16—C17179.18 (11)
C16—N2—C9—C10−74.12 (14)O1—C16—C17—C181.59 (17)
N1—N2—C9—C10103.27 (11)N2—C16—C17—C18−179.55 (10)
C16—N2—C9—C8164.49 (11)C16—C17—C18—C19−177.81 (11)
N1—N2—C9—C8−18.12 (12)

Hydrogen-bond geometry (Å, º)

D—H···AD—HH···AD···AD—H···A
C11—H11A···F1i0.952.373.1873 (17)144
C14—H14A···O1ii0.952.573.1832 (16)122
C5—H5A···Cg2iii0.952.683.5453 (15)152
C17—H17B···Cg1iv0.992.703.5488 (14)144

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB6918).

References

  • Bruker (2009). APEX2, SAINT and SADABSBruker AXS Inc., Madison, Wisconsin, USA.
  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107.
  • Fun, H.-K., Hemamalini, M., Samshuddin, S., Narayana, B. & Yathirajan, H. S. (2010). Acta Cryst. E66, o582–o583. [PMC free article] [PubMed]
  • Fun, H.-K., Loh, W.-S., Sapnakumari, M., Narayana, B. & Sarojini, B. K. (2012). Acta Cryst. E68, o2586. [PMC free article] [PubMed]
  • Fun, H.-K., Quah, C. K., Samshuddin, S., Narayana, B. & Sarojini, B. K. (2012). Acta Cryst. E68, o975. [PMC free article] [PubMed]
  • Samshuddin, S., Narayana, B., Baktir, Z., Akkurt, M. & Yathirajan, H. S. (2011). Der Pharma Chem. 3, 487–493.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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