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

doi:10.1107/S1600536812033351

Acta Crystallogr Sect E Struct Rep Online. 2012 August 1; 68(Pt 8): o2586.

Published online 2012 July 28. 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. Sarojini^c

^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.

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

This article has been cited by other articles in PMC.

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

). For related structures, see: Fun et al. (2010

, 2012

). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986

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

Experimental

Crystal data

C₁₇H₁₄BrFN₂O
M _r = 361.21
Monoclinic,
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 ) 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
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2009

); cell refinement: SAINT (Bruker, 2009

); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008

); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009

Table 1

Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812033351/cv5325sup1.cif

Click here to view.^{(25K, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033351/cv5325Isup2.hkl

Click here to view.^{(264K, 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.

Figures

Fig. 1.

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

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

C₁₇H₁₄BrFN₂O	F(000) = 728
M_r = 361.21	D_x = 1.598 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7995 reflections
a = 6.0973 (5) Å	θ = 3.3–32.4°
b = 12.3079 (11) Å	µ = 2.75 mm⁻¹
c = 20.1432 (16) Å	T = 100 K
β = 96.700 (1)°	Block, colourless
V = 1501.3 (2) Å³	0.35 × 0.29 × 0.12 mm
Z = 4

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer	5389 independent reflections
Radiation source: fine-focus sealed tube	4508 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
and ω scans	θ_max = 32.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.449, T_max = 0.735	k = −18→18
20560 measured reflections	l = −30→28

Refinement

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0284P)² + 0.4844P] where P = (F_o² + 2F_c²)/3
5389 reflections	(Δ/σ)_max = 0.002
200 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

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)

	x	y	z	U_iso*/U_eq
Br1	0.04341 (2)	0.791941 (11)	0.448115 (6)	0.02747 (5)
F1	−0.59388 (13)	1.16479 (7)	0.96048 (4)	0.02911 (17)
O1	0.64441 (14)	0.86820 (8)	0.74360 (4)	0.02269 (17)
N1	0.18952 (16)	0.95514 (8)	0.82286 (5)	0.01709 (17)
N2	0.33651 (16)	0.94281 (8)	0.77529 (5)	0.01819 (18)
C1	−0.12723 (19)	1.02079 (10)	0.90775 (6)	0.0197 (2)
H1A	−0.0275	0.9644	0.9231	0.024*
C2	−0.2902 (2)	1.05229 (10)	0.94636 (6)	0.0219 (2)
H2A	−0.3024	1.0189	0.9883	0.026*
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	−0.5265	1.2404	0.8468	0.024*
C5	−0.25649 (19)	1.15407 (9)	0.82441 (6)	0.0182 (2)
H5A	−0.2431	1.1896	0.7832	0.022*
C6	−0.10798 (18)	1.07118 (9)	0.84631 (5)	0.01613 (19)
C7	0.06512 (18)	1.03787 (9)	0.80585 (5)	0.01641 (19)
C8	0.1174 (2)	1.09452 (10)	0.74299 (6)	0.0204 (2)
H8A	0.1713	1.1694	0.7527	0.024*
H8B	−0.0138	1.0972	0.7091	0.024*
C9	0.30095 (19)	1.02199 (9)	0.71935 (6)	0.0182 (2)
H9A	0.4379	1.0659	0.7171	0.022*
C10	0.23654 (18)	0.96573 (9)	0.65297 (5)	0.01642 (19)
C11	0.38005 (19)	0.96669 (9)	0.60390 (6)	0.0182 (2)
H11A	0.5182	1.0028	0.6123	0.022*
C12	0.3230 (2)	0.91522 (10)	0.54268 (6)	0.0193 (2)
H12A	0.4217	0.9153	0.5095	0.023*
C13	0.1196 (2)	0.86390 (9)	0.53106 (6)	0.0188 (2)
C14	−0.02684 (19)	0.86179 (10)	0.57892 (6)	0.0204 (2)
H14A	−0.1656	0.8263	0.5701	0.025*
C15	0.03330 (19)	0.91257 (10)	0.64006 (6)	0.0193 (2)
H15A	−0.0648	0.9111	0.6734	0.023*
C16	0.50858 (18)	0.87211 (10)	0.78447 (6)	0.0179 (2)
C17	0.5186 (2)	0.79944 (10)	0.84496 (6)	0.0226 (2)
H17A	0.6488	0.7524	0.8465	0.034*
H17B	0.3851	0.7546	0.8422	0.034*
H17C	0.5285	0.8441	0.8855	0.034*

Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03694 (8)	0.02603 (7)	0.01781 (6)	−0.00295 (5)	−0.00372 (4)	−0.00310 (5)
F1	0.0272 (4)	0.0295 (4)	0.0332 (4)	0.0103 (3)	0.0145 (3)	0.0057 (3)
O1	0.0178 (4)	0.0292 (4)	0.0216 (4)	−0.0003 (3)	0.0047 (3)	−0.0060 (3)
N1	0.0168 (4)	0.0200 (4)	0.0149 (4)	0.0013 (3)	0.0036 (3)	−0.0005 (3)
N2	0.0192 (4)	0.0214 (4)	0.0148 (4)	0.0026 (4)	0.0052 (3)	0.0007 (3)
C1	0.0195 (5)	0.0191 (5)	0.0207 (5)	0.0037 (4)	0.0036 (4)	0.0029 (4)
C2	0.0220 (5)	0.0230 (5)	0.0217 (5)	0.0041 (4)	0.0068 (4)	0.0055 (4)
C3	0.0177 (5)	0.0195 (5)	0.0230 (5)	0.0014 (4)	0.0060 (4)	−0.0011 (4)
C4	0.0199 (5)	0.0161 (5)	0.0228 (5)	0.0031 (4)	0.0001 (4)	−0.0005 (4)
C5	0.0214 (5)	0.0162 (5)	0.0165 (5)	0.0011 (4)	0.0003 (4)	0.0004 (4)
C6	0.0167 (5)	0.0150 (4)	0.0165 (5)	−0.0004 (4)	0.0009 (4)	−0.0020 (4)
C7	0.0177 (5)	0.0164 (5)	0.0151 (5)	−0.0006 (4)	0.0019 (4)	−0.0011 (4)
C8	0.0266 (6)	0.0180 (5)	0.0171 (5)	0.0026 (4)	0.0051 (4)	0.0010 (4)
C9	0.0207 (5)	0.0184 (5)	0.0160 (5)	−0.0013 (4)	0.0038 (4)	0.0004 (4)
C10	0.0178 (5)	0.0162 (5)	0.0157 (5)	−0.0008 (4)	0.0037 (4)	0.0015 (4)
C11	0.0182 (5)	0.0195 (5)	0.0174 (5)	−0.0039 (4)	0.0044 (4)	0.0008 (4)
C12	0.0229 (5)	0.0202 (5)	0.0155 (5)	−0.0018 (4)	0.0055 (4)	0.0018 (4)
C13	0.0229 (5)	0.0174 (5)	0.0155 (5)	−0.0004 (4)	−0.0007 (4)	0.0006 (4)
C14	0.0172 (5)	0.0206 (5)	0.0231 (5)	−0.0025 (4)	0.0008 (4)	0.0008 (4)
C15	0.0173 (5)	0.0215 (5)	0.0199 (5)	−0.0017 (4)	0.0055 (4)	0.0010 (4)
C16	0.0157 (5)	0.0204 (5)	0.0173 (5)	−0.0007 (4)	0.0003 (4)	−0.0046 (4)
C17	0.0241 (5)	0.0243 (5)	0.0191 (5)	0.0057 (4)	0.0008 (4)	0.0001 (4)

Geometric parameters (Å, º)

Br1—C13	1.9003 (11)	C8—C9	1.5494 (16)
F1—C3	1.3622 (14)	C8—H8A	0.9900
O1—C16	1.2349 (14)	C8—H8B	0.9900
N1—C7	1.2919 (14)	C9—C10	1.5163 (16)
N1—N2	1.3947 (13)	C9—H9A	1.0000
N2—C16	1.3590 (15)	C10—C11	1.3945 (16)
N2—C9	1.4864 (15)	C10—C15	1.3987 (16)
C1—C2	1.3866 (16)	C11—C12	1.3940 (16)
C1—C6	1.4013 (16)	C11—H11A	0.9500
C1—H1A	0.9500	C12—C13	1.3867 (17)
C2—C3	1.3853 (16)	C12—H12A	0.9500
C2—H2A	0.9500	C13—C14	1.3887 (17)
C3—C4	1.3760 (17)	C14—C15	1.3916 (17)
C4—C5	1.3942 (17)	C14—H14A	0.9500
C4—H4A	0.9500	C15—H15A	0.9500
C5—C6	1.4008 (15)	C16—C17	1.5070 (17)
C5—H5A	0.9500	C17—H17A	0.9800
C6—C7	1.4653 (16)	C17—H17B	0.9800
C7—C8	1.5116 (16)	C17—H17C	0.9800

C7—N1—N2	107.94 (9)	N2—C9—C8	101.04 (9)
C16—N2—N1	121.60 (9)	C10—C9—C8	114.33 (10)
C16—N2—C9	124.40 (9)	N2—C9—H9A	109.8
N1—N2—C9	113.63 (9)	C10—C9—H9A	109.8
C2—C1—C6	120.72 (11)	C8—C9—H9A	109.8
C2—C1—H1A	119.6	C11—C10—C15	119.19 (10)
C6—C1—H1A	119.6	C11—C10—C9	120.12 (10)
C3—C2—C1	118.28 (11)	C15—C10—C9	120.69 (10)
C3—C2—H2A	120.9	C12—C11—C10	120.71 (11)
C1—C2—H2A	120.9	C12—C11—H11A	119.6
F1—C3—C4	118.69 (10)	C10—C11—H11A	119.6
F1—C3—C2	118.06 (11)	C13—C12—C11	118.83 (11)
C4—C3—C2	123.25 (11)	C13—C12—H12A	120.6
C3—C4—C5	117.78 (11)	C11—C12—H12A	120.6
C3—C4—H4A	121.1	C12—C13—C14	121.75 (11)
C5—C4—H4A	121.1	C12—C13—Br1	118.87 (9)
C4—C5—C6	121.09 (11)	C14—C13—Br1	119.37 (9)
C4—C5—H5A	119.5	C13—C14—C15	118.78 (11)
C6—C5—H5A	119.5	C13—C14—H14A	120.6
C5—C6—C1	118.87 (10)	C15—C14—H14A	120.6
C5—C6—C7	120.64 (10)	C14—C15—C10	120.73 (11)
C1—C6—C7	120.49 (10)	C14—C15—H15A	119.6
N1—C7—C6	120.77 (10)	C10—C15—H15A	119.6
N1—C7—C8	114.27 (10)	O1—C16—N2	120.09 (11)
C6—C7—C8	124.95 (10)	O1—C16—C17	123.28 (11)
C7—C8—C9	102.84 (9)	N2—C16—C17	116.61 (10)
C7—C8—H8A	111.2	C16—C17—H17A	109.5
C9—C8—H8A	111.2	C16—C17—H17B	109.5
C7—C8—H8B	111.2	H17A—C17—H17B	109.5
C9—C8—H8B	111.2	C16—C17—H17C	109.5
H8A—C8—H8B	109.1	H17A—C17—H17C	109.5
N2—C9—C10	111.65 (9)	H17B—C17—H17C	109.5

C7—N1—N2—C16	170.61 (10)	C16—N2—C9—C8	−168.23 (11)
C7—N1—N2—C9	−2.78 (13)	N1—N2—C9—C8	4.94 (12)
C6—C1—C2—C3	0.80 (19)	C7—C8—C9—N2	−4.85 (11)
C1—C2—C3—F1	−179.69 (11)	C7—C8—C9—C10	115.20 (10)
C1—C2—C3—C4	−0.44 (19)	N2—C9—C10—C11	−112.65 (12)
F1—C3—C4—C5	178.57 (10)	C8—C9—C10—C11	133.42 (11)
C2—C3—C4—C5	−0.67 (18)	N2—C9—C10—C15	67.46 (13)
C3—C4—C5—C6	1.44 (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—C7	179.11 (11)	C9—C10—C11—C12	179.94 (10)
C2—C1—C6—C5	−0.05 (18)	C10—C11—C12—C13	0.69 (18)
C2—C1—C6—C7	179.74 (11)	C11—C12—C13—C14	−0.57 (18)
N2—N1—C7—C6	179.71 (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—C15	178.47 (9)
C1—C6—C7—N1	6.49 (17)	C13—C14—C15—C10	0.61 (18)
C5—C6—C7—C8	6.99 (17)	C11—C10—C15—C14	−0.49 (17)
C1—C6—C7—C8	−172.79 (11)	C9—C10—C15—C14	179.39 (11)
N1—C7—C8—C9	3.93 (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—C10	69.83 (14)	N1—N2—C16—C17	6.25 (16)
N1—N2—C9—C10	−117.00 (10)	C9—N2—C16—C17	178.90 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1ⁱ	0.95	2.45	3.2772 (15)	146
C14—H14A···F1ⁱⁱ	0.95	2.50	3.3806 (15)	153
C15—H15A···O1ⁱⁱⁱ	0.95	2.45	3.3800 (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