PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. Aug 1, 2012; 68(Pt 8): o2586.
Published online Jul 28, 2012. doi:  10.1107/S1600536812033351
PMCID: PMC3415024
1-[5-(4-Bromo­phen­yl)-3-(4-fluoro­phen­yl)-4,5-dihydro-1H-pyrazol-1-yl]ethanone
Hoong-Kun Fun,a* Wan-Sin Loh,a§ M. Sapnakumari,b B. Narayana,b and B. K. Sarojinic
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India
cDepartment of Chemistry, P.A. College of Engineering, Nadupadavu, Mangalore 574 153, India
Correspondence e-mail: hkfun/at/usm.my
Thomson Reuters ResearcherID: A-3561-2009.
§Thomson Reuters ResearcherID: C-7581-2009.
Received July 19, 2012; Accepted July 24, 2012.
Abstract
In the title mol­ecule, C17H14BrFN2O, the benzene rings form dihedral angles of 6.58 (6) and 85.31 (6)° with the mean plane of the 4,5-dihydro-1H-pyrazole ring (r.m.s. deviation = 0.0231 Å). The latter ring is planar with a maximum deviation of 0.032 (1) Å The dihedral angle between the benzene rings is 78.75 (6)°. In the crystal, weak C—H(...)O and C—H(...)F hydrogen bonds link the mol­ecules into corrugated layers parallel to the ab plane.
Related literature  
For our work on the synthesis of pyrazoline derivatives, see: Samshuddin et al. (2011 [triangle]). For related structures, see: Fun et al. (2010 [triangle], 2012 [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-o2586-scheme1.jpg Object name is e-68-o2586-scheme1.jpg
Crystal data  
  • C17H14BrFN2O
  • M r = 361.21
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-68-o2586-efi1.jpg
  • a = 6.0973 (5) Å
  • b = 12.3079 (11) Å
  • c = 20.1432 (16) Å
  • β = 96.700 (1)°
  • V = 1501.3 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.75 mm−1
  • T = 100 K
  • 0.35 × 0.29 × 0.12 mm
Data collection  
  • Bruker SMART APEXII DUO CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2009 [triangle]) T min = 0.449, T max = 0.735
  • 20560 measured reflections
  • 5389 independent reflections
  • 4508 reflections with I > 2σ(I)
  • R int = 0.026
Refinement  
  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.064
  • S = 1.04
  • 5389 reflections
  • 200 parameters
  • H-atom parameters constrained
  • Δρmax = 0.50 e Å−3
  • Δρmin = −0.25 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
Table 1
Hydrogen-bond geometry (Å, °)
Supplementary Material
Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812033351/cv5325sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033351/cv5325Isup2.hkl
Supplementary material file. DOI: 10.1107/S1600536812033351/cv5325Isup3.cml
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
HKF and WSL thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). WSL also thanks the Malaysian Government and USM for the post of Research Officer under the Research University Grant (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 the 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 two benzene rings (C1–C6 & C10–C15) form dihedral angles of 6.58 (6) and 85.31 (6)°, respectively, with the mean plane of 4,5-dihydro-1H-pyrazole ring (N1/N2/C7–C9, r.m.s. deviation = 0.0231 Å). The dihedral angle between the two benzene rings is 78.75 (6)°. Bond lengths and angles are comparable with those in the related structures (Fun et al., 2010, 2012).
In the crystal packing (Fig. 2), intermolecular C—H···O and C—H···F hydrogen bonds (Table 1) link the molecules into corrugated layers parallel to the ab plane.
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 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-crystal was grown from acetone by slow evaporation method. M.p.: 372–374 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 1.00 Å]. A rotating group model was applied to the methyl group. In the final refinement, ten outliners were omitted, namely - 2 0 8, 1 4 2, 1 0 4, -2 7 5, -4 2 9, -3 4 9, -1 8 1, -2 2 4, 1 8 0 and 1 1 4 , respectively.
Figures
Fig. 1.
Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids.
Fig. 2.
Fig. 2.
A portion of the crystal packing viewed along the a axis. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.
Crystal data
C17H14BrFN2OF(000) = 728
Mr = 361.21Dx = 1.598 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7995 reflections
a = 6.0973 (5) Åθ = 3.3–32.4°
b = 12.3079 (11) ŵ = 2.75 mm1
c = 20.1432 (16) ÅT = 100 K
β = 96.700 (1)°Block, colourless
V = 1501.3 (2) Å30.35 × 0.29 × 0.12 mm
Z = 4
Data collection
Bruker SMART APEXII DUO CCD area-detector diffractometer5389 independent reflections
Radiation source: fine-focus sealed tube4508 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
[var phi] and ω scansθmax = 32.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)h = −9→9
Tmin = 0.449, Tmax = 0.735k = −18→18
20560 measured reflectionsl = −30→28
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)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0284P)2 + 0.4844P] where P = (Fo2 + 2Fc2)/3
5389 reflections(Δ/σ)max = 0.002
200 parametersΔρmax = 0.50 e Å3
0 restraintsΔρmin = −0.25 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
Br10.04341 (2)0.791941 (11)0.448115 (6)0.02747 (5)
F1−0.59388 (13)1.16479 (7)0.96048 (4)0.02911 (17)
O10.64441 (14)0.86820 (8)0.74360 (4)0.02269 (17)
N10.18952 (16)0.95514 (8)0.82286 (5)0.01709 (17)
N20.33651 (16)0.94281 (8)0.77529 (5)0.01819 (18)
C1−0.12723 (19)1.02079 (10)0.90775 (6)0.0197 (2)
H1A−0.02750.96440.92310.024*
C2−0.2902 (2)1.05229 (10)0.94636 (6)0.0219 (2)
H2A−0.30241.01890.98830.026*
C3−0.43476 (19)1.13377 (10)0.92222 (6)0.0198 (2)
C4−0.42365 (19)1.18535 (9)0.86209 (6)0.0198 (2)
H4A−0.52651.24040.84680.024*
C5−0.25649 (19)1.15407 (9)0.82441 (6)0.0182 (2)
H5A−0.24311.18960.78320.022*
C6−0.10798 (18)1.07118 (9)0.84631 (5)0.01613 (19)
C70.06512 (18)1.03787 (9)0.80585 (5)0.01641 (19)
C80.1174 (2)1.09452 (10)0.74299 (6)0.0204 (2)
H8A0.17131.16940.75270.024*
H8B−0.01381.09720.70910.024*
C90.30095 (19)1.02199 (9)0.71935 (6)0.0182 (2)
H9A0.43791.06590.71710.022*
C100.23654 (18)0.96573 (9)0.65297 (5)0.01642 (19)
C110.38005 (19)0.96669 (9)0.60390 (6)0.0182 (2)
H11A0.51821.00280.61230.022*
C120.3230 (2)0.91522 (10)0.54268 (6)0.0193 (2)
H12A0.42170.91530.50950.023*
C130.1196 (2)0.86390 (9)0.53106 (6)0.0188 (2)
C14−0.02684 (19)0.86179 (10)0.57892 (6)0.0204 (2)
H14A−0.16560.82630.57010.025*
C150.03330 (19)0.91257 (10)0.64006 (6)0.0193 (2)
H15A−0.06480.91110.67340.023*
C160.50858 (18)0.87211 (10)0.78447 (6)0.0179 (2)
C170.5186 (2)0.79944 (10)0.84496 (6)0.0226 (2)
H17A0.64880.75240.84650.034*
H17B0.38510.75460.84220.034*
H17C0.52850.84410.88550.034*
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
Br10.03694 (8)0.02603 (7)0.01781 (6)−0.00295 (5)−0.00372 (4)−0.00310 (5)
F10.0272 (4)0.0295 (4)0.0332 (4)0.0103 (3)0.0145 (3)0.0057 (3)
O10.0178 (4)0.0292 (4)0.0216 (4)−0.0003 (3)0.0047 (3)−0.0060 (3)
N10.0168 (4)0.0200 (4)0.0149 (4)0.0013 (3)0.0036 (3)−0.0005 (3)
N20.0192 (4)0.0214 (4)0.0148 (4)0.0026 (4)0.0052 (3)0.0007 (3)
C10.0195 (5)0.0191 (5)0.0207 (5)0.0037 (4)0.0036 (4)0.0029 (4)
C20.0220 (5)0.0230 (5)0.0217 (5)0.0041 (4)0.0068 (4)0.0055 (4)
C30.0177 (5)0.0195 (5)0.0230 (5)0.0014 (4)0.0060 (4)−0.0011 (4)
C40.0199 (5)0.0161 (5)0.0228 (5)0.0031 (4)0.0001 (4)−0.0005 (4)
C50.0214 (5)0.0162 (5)0.0165 (5)0.0011 (4)0.0003 (4)0.0004 (4)
C60.0167 (5)0.0150 (4)0.0165 (5)−0.0004 (4)0.0009 (4)−0.0020 (4)
C70.0177 (5)0.0164 (5)0.0151 (5)−0.0006 (4)0.0019 (4)−0.0011 (4)
C80.0266 (6)0.0180 (5)0.0171 (5)0.0026 (4)0.0051 (4)0.0010 (4)
C90.0207 (5)0.0184 (5)0.0160 (5)−0.0013 (4)0.0038 (4)0.0004 (4)
C100.0178 (5)0.0162 (5)0.0157 (5)−0.0008 (4)0.0037 (4)0.0015 (4)
C110.0182 (5)0.0195 (5)0.0174 (5)−0.0039 (4)0.0044 (4)0.0008 (4)
C120.0229 (5)0.0202 (5)0.0155 (5)−0.0018 (4)0.0055 (4)0.0018 (4)
C130.0229 (5)0.0174 (5)0.0155 (5)−0.0004 (4)−0.0007 (4)0.0006 (4)
C140.0172 (5)0.0206 (5)0.0231 (5)−0.0025 (4)0.0008 (4)0.0008 (4)
C150.0173 (5)0.0215 (5)0.0199 (5)−0.0017 (4)0.0055 (4)0.0010 (4)
C160.0157 (5)0.0204 (5)0.0173 (5)−0.0007 (4)0.0003 (4)−0.0046 (4)
C170.0241 (5)0.0243 (5)0.0191 (5)0.0057 (4)0.0008 (4)0.0001 (4)
Geometric parameters (Å, º)
Br1—C131.9003 (11)C8—C91.5494 (16)
F1—C31.3622 (14)C8—H8A0.9900
O1—C161.2349 (14)C8—H8B0.9900
N1—C71.2919 (14)C9—C101.5163 (16)
N1—N21.3947 (13)C9—H9A1.0000
N2—C161.3590 (15)C10—C111.3945 (16)
N2—C91.4864 (15)C10—C151.3987 (16)
C1—C21.3866 (16)C11—C121.3940 (16)
C1—C61.4013 (16)C11—H11A0.9500
C1—H1A0.9500C12—C131.3867 (17)
C2—C31.3853 (16)C12—H12A0.9500
C2—H2A0.9500C13—C141.3887 (17)
C3—C41.3760 (17)C14—C151.3916 (17)
C4—C51.3942 (17)C14—H14A0.9500
C4—H4A0.9500C15—H15A0.9500
C5—C61.4008 (15)C16—C171.5070 (17)
C5—H5A0.9500C17—H17A0.9800
C6—C71.4653 (16)C17—H17B0.9800
C7—C81.5116 (16)C17—H17C0.9800
C7—N1—N2107.94 (9)N2—C9—C8101.04 (9)
C16—N2—N1121.60 (9)C10—C9—C8114.33 (10)
C16—N2—C9124.40 (9)N2—C9—H9A109.8
N1—N2—C9113.63 (9)C10—C9—H9A109.8
C2—C1—C6120.72 (11)C8—C9—H9A109.8
C2—C1—H1A119.6C11—C10—C15119.19 (10)
C6—C1—H1A119.6C11—C10—C9120.12 (10)
C3—C2—C1118.28 (11)C15—C10—C9120.69 (10)
C3—C2—H2A120.9C12—C11—C10120.71 (11)
C1—C2—H2A120.9C12—C11—H11A119.6
F1—C3—C4118.69 (10)C10—C11—H11A119.6
F1—C3—C2118.06 (11)C13—C12—C11118.83 (11)
C4—C3—C2123.25 (11)C13—C12—H12A120.6
C3—C4—C5117.78 (11)C11—C12—H12A120.6
C3—C4—H4A121.1C12—C13—C14121.75 (11)
C5—C4—H4A121.1C12—C13—Br1118.87 (9)
C4—C5—C6121.09 (11)C14—C13—Br1119.37 (9)
C4—C5—H5A119.5C13—C14—C15118.78 (11)
C6—C5—H5A119.5C13—C14—H14A120.6
C5—C6—C1118.87 (10)C15—C14—H14A120.6
C5—C6—C7120.64 (10)C14—C15—C10120.73 (11)
C1—C6—C7120.49 (10)C14—C15—H15A119.6
N1—C7—C6120.77 (10)C10—C15—H15A119.6
N1—C7—C8114.27 (10)O1—C16—N2120.09 (11)
C6—C7—C8124.95 (10)O1—C16—C17123.28 (11)
C7—C8—C9102.84 (9)N2—C16—C17116.61 (10)
C7—C8—H8A111.2C16—C17—H17A109.5
C9—C8—H8A111.2C16—C17—H17B109.5
C7—C8—H8B111.2H17A—C17—H17B109.5
C9—C8—H8B111.2C16—C17—H17C109.5
H8A—C8—H8B109.1H17A—C17—H17C109.5
N2—C9—C10111.65 (9)H17B—C17—H17C109.5
C7—N1—N2—C16170.61 (10)C16—N2—C9—C8−168.23 (11)
C7—N1—N2—C9−2.78 (13)N1—N2—C9—C84.94 (12)
C6—C1—C2—C30.80 (19)C7—C8—C9—N2−4.85 (11)
C1—C2—C3—F1−179.69 (11)C7—C8—C9—C10115.20 (10)
C1—C2—C3—C4−0.44 (19)N2—C9—C10—C11−112.65 (12)
F1—C3—C4—C5178.57 (10)C8—C9—C10—C11133.42 (11)
C2—C3—C4—C5−0.67 (18)N2—C9—C10—C1567.46 (13)
C3—C4—C5—C61.44 (17)C8—C9—C10—C15−46.47 (15)
C4—C5—C6—C1−1.10 (17)C15—C10—C11—C12−0.17 (17)
C4—C5—C6—C7179.11 (11)C9—C10—C11—C12179.94 (10)
C2—C1—C6—C5−0.05 (18)C10—C11—C12—C130.69 (18)
C2—C1—C6—C7179.74 (11)C11—C12—C13—C14−0.57 (18)
N2—N1—C7—C6179.71 (10)C11—C12—C13—Br1−179.12 (9)
N2—N1—C7—C8−0.93 (13)C12—C13—C14—C15−0.08 (18)
C5—C6—C7—N1−173.72 (11)Br1—C13—C14—C15178.47 (9)
C1—C6—C7—N16.49 (17)C13—C14—C15—C100.61 (18)
C5—C6—C7—C86.99 (17)C11—C10—C15—C14−0.49 (17)
C1—C6—C7—C8−172.79 (11)C9—C10—C15—C14179.39 (11)
N1—C7—C8—C93.93 (13)N1—N2—C16—O1−175.15 (10)
C6—C7—C8—C9−176.74 (10)C9—N2—C16—O1−2.50 (17)
C16—N2—C9—C1069.83 (14)N1—N2—C16—C176.25 (16)
N1—N2—C9—C10−117.00 (10)C9—N2—C16—C17178.90 (10)
Hydrogen-bond geometry (Å, º)
D—H···AD—HH···AD···AD—H···A
C4—H4A···O1i0.952.453.2772 (15)146
C14—H14A···F1ii0.952.503.3806 (15)153
C15—H15A···O1iii0.952.453.3800 (15)166
Symmetry codes: (i) −x, y+1/2, −z+3/2; (ii) −x−1, y−1/2, −z+3/2; (iii) x−1, y, z.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV5325).
References
  • Bruker (2009). APEX2, SAINT and SADABS Bruker 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., 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]
Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of
International Union of Crystallography