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Acta Crystallogr Sect E Struct Rep Online. Nov 1, 2008; 64(Pt 11): o2160.
Published online Oct 22, 2008. doi:  10.1107/S1600536808033837
PMCID: PMC2959565
1-[3-(2,4-Dichloro-5-fluoro­phen­yl)-5-(3-methyl-2-thien­yl)-4,5-dihydro-1H-pyrazol-1-yl]ethanone
N. Anuradha,a A. Thiruvalluvar,a* M. Mahalinga,b and R. J. Butcherc
aPG Research Department of Physics, Rajah Serfoji Government College (Autonomous), Thanjavur 613 005, Tamil Nadu, India
bSeQuent Scientific Limited, 120 A&B Industrial Area, Baikampady, New Mangalore 575 011, India
cDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
Correspondence e-mail: athiru/at/vsnl.net
Received October 12, 2008; Accepted October 16, 2008.
In the title mol­ecule, C16H13Cl2FN2OS, the dihedral angle between the thio­phene and benzene rings is 80.34 (12)°. The pyrazoline ring is in an envelope conformation, and the plane through the four coplanar atoms makes dihedral angles of 85.13 (9) and 6.89 (10)° with the thio­phene and benzene rings, respectively. The C and O atoms of the acetyl group are nearly coplanar with the attached pyrazoline ring. In the crystal structure, inversion dimers arise from pairs of inter­molecular C—H(...)O hydrogen bonds. A short inter­molecular Cl(...)S contact of 3.4250 (13) Å is also found.
Related literature
For a related crystal structure, see: Thiruvalluvar et al. (2007 [triangle]).
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Object name is e-64-o2160-scheme1.jpg Object name is e-64-o2160-scheme1.jpg
Crystal data
  • C16H13Cl2FN2OS
  • M r = 371.25
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2160-efi1.jpg
  • a = 7.2240 (5) Å
  • b = 8.8642 (4) Å
  • c = 14.0518 (9) Å
  • α = 100.794 (5)°
  • β = 103.307 (6)°
  • γ = 101.003 (5)°
  • V = 833.99 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.53 mm−1
  • T = 295 (2) K
  • 0.52 × 0.43 × 0.35 mm
Data collection
  • Oxford Diffraction R Gemini diffractometer
  • Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 [triangle]) T min = 0.786, T max = 1.000 (expected range = 0.654–0.831)
  • 12358 measured reflections
  • 5445 independent reflections
  • 3028 reflections with I > 2σ(I)
  • R int = 0.020
Refinement
  • R[F 2 > 2σ(F 2)] = 0.051
  • wR(F 2) = 0.179
  • S = 1.12
  • 5445 reflections
  • 210 parameters
  • H-atom parameters constrained
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.39 e Å−3
Data collection: CrysAlis CCD (Oxford Diffraction, 2008 [triangle]); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 [triangle]); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: PLATON (Spek, 2003 [triangle]).
Table 1
Table 1
Hydrogen-bond geometry (Å, °)
Supplementary Material
Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808033837/wn2286sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536808033837/wn2286Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Acknowledgments
AT thanks the UGC, India, for the award of a Minor Research Project [file No. MRP-2355/06(UGC-SERO), Link No. 2355, 10/01/2007]. RJB acknowledges the NSF-MRI program for funding to purchase the X-ray CCD diffractometer.
supplementary crystallographic information
Comment
A great deal of attention has been paid to the synthesis and structural aspects of pyrazolines, as witnessed by continued activity in this area (Thiruvalluvar et al., 2007).
In the title molecule, C16H13Cl2FN2OS, Fig.1., the dihedral angle between the thiophene and benzene rings is 80.34 (12)°. The pyrazoline ring is in an envelope conformation and the plane through the four coplanar atoms makes dihedral angles of 85.13 (9)° and 6.89 (10)° with the thiophene and benzene rings, respectively. The acetyl group, except for the hydrogen atoms, is nearly coplanar with the attached pyrazoline ring. An intermolecular C2—H2A···O1(-1 - x, 1 - y, -z) hydrogen bond is found in the crystal structure (Table 1). Further, a short intermolecular Cl4···S21(1-x,1-y,1-z) contact of 3.4250 (13) Å is also found in the crystal structure.
Experimental
A mixture of 1-(2,4-dichloro-5-fluorophenyl)-3-(3-methylthien-2-yl) prop-2-en-1-one (5 g, 0.016 mol) and a molar equivalent of hydrazine hydrate (80%) in glacial acetic acid (25 ml) was heated on a water bath at 363–365 K for 5–6 h. The reaction mass was then poured into ice-cold water. The solid obtained was filtered, washed with water, dried and crystallized from methanol to yield the title compound. Yield 5.5 g (93.5%).
Refinement
H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93, 0.96, 0.97 and 0.98 Å for Csp2, methyl, methylene and methine C, respectively; Uiso(H) = kUeq(C), where k = 1.5 for methyl and 1.2 for all other H atoms.
Figures
Fig. 1.
Fig. 1.
The molecular structure of the title compound, showing the atom-numbering scheme and displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radius.
Fig. 2.
Fig. 2.
The packing of the title compound, viewed down the a axis. Dashed lines indicate hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted.
Crystal data
C16H13Cl2FN2OSZ = 2
Mr = 371.25F(000) = 380
Triclinic, P1Dx = 1.478 Mg m3
Hall symbol: -P 1Melting point: 369.5 K
a = 7.2240 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.8642 (4) ÅCell parameters from 4639 reflections
c = 14.0518 (9) Åθ = 4.6–32.4°
α = 100.794 (5)°µ = 0.53 mm1
β = 103.307 (6)°T = 295 K
γ = 101.003 (5)°Chunk, pale-yellow
V = 833.99 (10) Å30.52 × 0.43 × 0.35 mm
Data collection
Oxford Diffraction R Gemini diffractometer5445 independent reflections
Radiation source: fine-focus sealed tube3028 reflections with I > 2σ(I)
graphiteRint = 0.020
Detector resolution: 10.5081 pixels mm-1θmax = 32.5°, θmin = 4.6°
[var phi] and ω scansh = −10→10
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)k = −13→13
Tmin = 0.786, Tmax = 1.000l = −21→21
12358 measured reflections
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.179H-atom parameters constrained
S = 1.12w = 1/[σ2(Fo2) + (0.083P)2 + 0.1183P] where P = (Fo2 + 2Fc2)/3
5445 reflections(Δ/σ)max = 0.001
210 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = −0.39 e Å3
Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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 > 2σ(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
Cl20.31301 (12)0.93549 (8)0.58594 (5)0.0696 (3)
Cl40.45313 (12)0.40815 (13)0.68787 (6)0.0875 (4)
S210.33962 (10)0.82555 (8)0.17261 (5)0.0572 (2)
F50.2322 (3)0.25555 (19)0.47920 (15)0.0820 (7)
O1−0.2572 (3)0.7121 (2)0.06719 (14)0.0721 (7)
N1−0.0630 (3)0.6973 (2)0.21112 (13)0.0432 (5)
N20.0012 (3)0.6131 (2)0.28019 (13)0.0388 (5)
C1−0.1967 (4)0.6281 (3)0.12037 (17)0.0499 (7)
C2−0.2599 (5)0.4503 (3)0.0905 (2)0.0753 (10)
C30.1042 (3)0.7120 (2)0.36402 (15)0.0352 (6)
C40.1162 (4)0.8829 (3)0.36061 (16)0.0460 (7)
C50.0216 (3)0.8696 (2)0.24839 (16)0.0434 (7)
C110.1899 (3)0.6464 (3)0.44812 (15)0.0383 (6)
C120.2871 (3)0.7332 (3)0.54694 (16)0.0464 (7)
C130.3677 (3)0.6604 (4)0.62105 (18)0.0574 (9)
C140.3507 (4)0.5009 (4)0.5990 (2)0.0574 (9)
C150.2522 (4)0.4140 (3)0.5020 (2)0.0533 (8)
C160.1750 (3)0.4835 (3)0.42821 (18)0.0457 (7)
C220.1646 (3)0.9275 (3)0.19146 (16)0.0429 (6)
C230.1824 (4)1.0568 (3)0.15275 (18)0.0514 (8)
C240.3412 (4)1.0737 (3)0.10905 (19)0.0629 (9)
C250.4390 (4)0.9588 (4)0.1136 (2)0.0634 (10)
C260.0455 (5)1.1637 (3)0.1527 (3)0.0800 (11)
H2A−0.393920.417330.050150.1130*
H2B−0.248250.410200.149970.1130*
H2C−0.177920.409870.052400.1130*
H4A0.251240.944540.381960.0552*
H4B0.043430.930700.402770.0552*
H5−0.083330.925750.241490.0520*
H130.433380.721140.685880.0688*
H160.111300.421080.363560.0549*
H240.375141.156930.079730.0755*
H250.546020.952960.088130.0761*
H26A−0.019731.153000.204270.1200*
H26B−0.050211.135430.088240.1200*
H26C0.118381.271470.165570.1200*
Atomic displacement parameters (Å2)
U11U22U33U12U13U23
Cl20.0784 (5)0.0659 (4)0.0470 (4)0.0100 (3)0.0044 (3)−0.0045 (3)
Cl40.0679 (5)0.1559 (8)0.0819 (5)0.0599 (5)0.0340 (4)0.0827 (5)
S210.0645 (4)0.0652 (4)0.0544 (4)0.0279 (3)0.0223 (3)0.0251 (3)
F50.0976 (14)0.0656 (10)0.1059 (14)0.0393 (10)0.0337 (11)0.0495 (10)
O10.0727 (13)0.0737 (12)0.0585 (11)0.0147 (10)−0.0122 (9)0.0292 (10)
N10.0460 (10)0.0385 (9)0.0402 (9)0.0047 (8)0.0017 (8)0.0163 (7)
N20.0357 (9)0.0400 (9)0.0378 (9)0.0061 (7)0.0032 (7)0.0146 (7)
C10.0470 (13)0.0536 (13)0.0429 (12)0.0087 (10)0.0013 (10)0.0142 (10)
C20.082 (2)0.0553 (15)0.0583 (16)0.0023 (14)−0.0197 (14)0.0040 (13)
C30.0335 (10)0.0376 (10)0.0371 (10)0.0093 (8)0.0117 (8)0.0123 (8)
C40.0565 (14)0.0401 (11)0.0394 (11)0.0083 (10)0.0135 (10)0.0083 (9)
C50.0493 (12)0.0368 (10)0.0445 (12)0.0116 (9)0.0088 (9)0.0150 (9)
C110.0345 (10)0.0487 (11)0.0353 (10)0.0117 (9)0.0116 (8)0.0147 (9)
C120.0371 (11)0.0611 (14)0.0386 (11)0.0083 (10)0.0095 (9)0.0115 (10)
C130.0408 (12)0.095 (2)0.0397 (12)0.0185 (13)0.0095 (10)0.0242 (13)
C140.0424 (12)0.093 (2)0.0593 (15)0.0309 (13)0.0232 (11)0.0465 (14)
C150.0467 (13)0.0635 (15)0.0669 (16)0.0231 (11)0.0255 (11)0.0354 (12)
C160.0435 (12)0.0524 (12)0.0468 (12)0.0146 (10)0.0147 (9)0.0195 (10)
C220.0489 (12)0.0388 (10)0.0373 (10)0.0064 (9)0.0049 (9)0.0133 (8)
C230.0632 (15)0.0427 (12)0.0436 (12)0.0093 (10)0.0059 (11)0.0136 (10)
C240.0743 (18)0.0605 (15)0.0468 (14)−0.0042 (13)0.0134 (12)0.0209 (12)
C250.0626 (17)0.0799 (19)0.0507 (14)0.0115 (14)0.0215 (12)0.0215 (13)
C260.100 (2)0.0523 (15)0.085 (2)0.0327 (16)0.0071 (18)0.0184 (15)
Geometric parameters (Å, °)
Cl2—C121.734 (3)C14—C151.382 (4)
Cl4—C141.725 (3)C15—C161.367 (4)
S21—C221.728 (2)C22—C231.355 (4)
S21—C251.707 (3)C23—C241.417 (4)
F5—C151.352 (3)C23—C261.495 (4)
O1—C11.219 (3)C24—C251.349 (4)
N1—N21.382 (3)C2—H2A0.9600
N1—C11.360 (3)C2—H2B0.9600
N1—C51.476 (3)C2—H2C0.9600
N2—C31.293 (3)C4—H4A0.9700
C1—C21.503 (4)C4—H4B0.9700
C3—C41.511 (3)C5—H50.9800
C3—C111.475 (3)C13—H130.9300
C4—C51.540 (3)C16—H160.9300
C5—C221.517 (3)C24—H240.9300
C11—C121.399 (3)C25—H250.9300
C11—C161.397 (4)C26—H26A0.9600
C12—C131.399 (4)C26—H26B0.9600
C13—C141.365 (5)C26—H26C0.9600
Cl2···C43.064 (2)C11···C15ii3.391 (4)
Cl2···S21i3.6953 (10)C14···C15iii3.502 (4)
Cl4···N1ii3.488 (2)C14···C16iii3.514 (4)
Cl4···N2ii3.389 (2)C15···C14iii3.502 (4)
Cl4···C11iii3.596 (2)C15···C11ii3.391 (4)
Cl4···C16iii3.524 (3)C16···Cl4iii3.524 (3)
Cl4···F52.917 (2)C16···C14iii3.514 (4)
Cl4···S21iii3.4250 (13)C16···C16ii3.600 (3)
Cl4···C1ii3.632 (3)C22···O13.172 (3)
Cl2···H4A2.8200C24···O1vi3.408 (3)
Cl2···H4B2.8400C5···H26A2.7500
Cl2···H4Ai3.0200C24···H13i3.0000
Cl2···H4Biv3.0600C24···H25x3.0400
S21···N13.121 (2)C24···H26Bvi3.0700
S21···C33.689 (2)C25···H25x3.1000
S21···Cl2i3.6953 (10)C26···H52.7600
S21···Cl4iii3.4250 (13)H2A···O1viii2.5800
S21···H4A3.1800H2B···N22.4200
F5···Cl42.917 (2)H4A···Cl22.8200
F5···C4v3.260 (3)H4A···S213.1800
F5···H4Bv2.8200H4A···Cl2i3.0200
O1···C223.172 (3)H4B···Cl22.8400
O1···C24vi3.408 (3)H4B···F5ix2.8200
O1···H52.6600H4B···Cl2iv3.0600
O1···H25vii2.7900H5···O12.6600
O1···H2Aviii2.5800H5···C262.7600
O1···H24vi2.6100H5···H26A2.1700
N1···S213.121 (2)H13···C24i3.0000
N1···Cl4ii3.488 (2)H16···N22.4000
N2···Cl4ii3.389 (2)H24···O1vi2.6100
N2···H2B2.4200H25···O1xi2.7900
N2···H162.4000H25···C24x3.0400
C1···Cl4ii3.632 (3)H25···C25x3.1000
C3···S213.689 (2)H26A···C52.7500
C4···Cl23.064 (2)H26A···H52.1700
C4···F5ix3.260 (3)H26B···C24vi3.0700
C11···Cl4iii3.596 (2)
C22—S21—C2591.98 (14)C22—C23—C26123.8 (3)
N2—N1—C1123.08 (19)C24—C23—C26124.6 (3)
N2—N1—C5112.89 (16)C23—C24—C25114.3 (3)
C1—N1—C5123.97 (19)S21—C25—C24110.8 (2)
N1—N2—C3108.80 (17)C1—C2—H2A109.00
O1—C1—N1118.9 (2)C1—C2—H2B109.00
O1—C1—C2123.5 (2)C1—C2—H2C109.00
N1—C1—C2117.6 (2)H2A—C2—H2B109.00
N2—C3—C4113.05 (18)H2A—C2—H2C110.00
N2—C3—C11117.69 (18)H2B—C2—H2C109.00
C4—C3—C11129.25 (19)C3—C4—H4A111.00
C3—C4—C5102.60 (17)C3—C4—H4B111.00
N1—C5—C4101.26 (16)C5—C4—H4A111.00
N1—C5—C22110.98 (18)C5—C4—H4B111.00
C4—C5—C22114.48 (19)H4A—C4—H4B109.00
C3—C11—C12125.8 (2)N1—C5—H5110.00
C3—C11—C16117.75 (19)C4—C5—H5110.00
C12—C11—C16116.5 (2)C22—C5—H5110.00
Cl2—C12—C11122.69 (19)C12—C13—H13120.00
Cl2—C12—C13115.80 (19)C14—C13—H13120.00
C11—C12—C13121.5 (2)C11—C16—H16119.00
C12—C13—C14120.5 (2)C15—C16—H16119.00
Cl4—C14—C13121.7 (2)C23—C24—H24123.00
Cl4—C14—C15120.0 (3)C25—C24—H24123.00
C13—C14—C15118.3 (3)S21—C25—H25125.00
F5—C15—C14119.0 (3)C24—C25—H25125.00
F5—C15—C16119.0 (2)C23—C26—H26A110.00
C14—C15—C16122.0 (3)C23—C26—H26B110.00
C11—C16—C15121.2 (2)C23—C26—H26C109.00
S21—C22—C5119.58 (18)H26A—C26—H26B109.00
S21—C22—C23111.36 (19)H26A—C26—H26C109.00
C5—C22—C23129.0 (2)H26B—C26—H26C109.00
C22—C23—C24111.6 (2)
C25—S21—C22—C5−177.60 (19)C4—C5—C22—S2166.8 (2)
C25—S21—C22—C230.6 (2)C4—C5—C22—C23−111.1 (3)
C22—S21—C25—C24−0.2 (2)C3—C11—C12—Cl22.4 (3)
C1—N1—N2—C3−170.7 (2)C3—C11—C12—C13−178.4 (2)
C5—N1—N2—C36.6 (3)C16—C11—C12—Cl2−178.11 (18)
N2—N1—C1—O1174.2 (2)C16—C11—C12—C131.1 (3)
C5—N1—C1—O1−2.8 (4)C3—C11—C16—C15179.5 (2)
N2—N1—C1—C2−6.6 (4)C12—C11—C16—C15−0.1 (4)
C5—N1—C1—C2176.4 (2)Cl2—C12—C13—C14178.2 (2)
N2—N1—C5—C4−11.3 (3)C11—C12—C13—C14−1.0 (4)
C1—N1—C5—C4166.0 (2)C12—C13—C14—Cl4178.5 (2)
N2—N1—C5—C22110.7 (2)C12—C13—C14—C150.0 (4)
C1—N1—C5—C22−72.1 (3)Cl4—C14—C15—F52.2 (4)
N1—N2—C3—C11−179.1 (2)Cl4—C14—C15—C16−177.6 (2)
N1—N2—C3—C41.6 (3)C13—C14—C15—F5−179.3 (3)
N2—C3—C4—C5−8.4 (3)C13—C14—C15—C161.0 (4)
C4—C3—C11—C16−173.1 (2)F5—C15—C16—C11179.3 (2)
N2—C3—C11—C12−172.7 (2)C14—C15—C16—C11−1.0 (4)
N2—C3—C11—C167.8 (3)S21—C22—C23—C24−0.9 (3)
C11—C3—C4—C5172.4 (2)S21—C22—C23—C26176.7 (2)
C4—C3—C11—C126.4 (4)C5—C22—C23—C24177.1 (2)
C3—C4—C5—N110.9 (2)C5—C22—C23—C26−5.3 (4)
C3—C4—C5—C22−108.6 (2)C22—C23—C24—C250.8 (3)
N1—C5—C22—S21−47.0 (2)C26—C23—C24—C25−176.8 (3)
N1—C5—C22—C23135.1 (2)C23—C24—C25—S21−0.3 (3)
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x, −y+2, −z+1; (v) x, y−1, z; (vi) −x, −y+2, −z; (vii) x−1, y, z; (viii) −x−1, −y+1, −z; (ix) x, y+1, z; (x) −x+1, −y+2, −z; (xi) x+1, y, z.
Hydrogen-bond geometry (Å, °)
D—H···AD—HH···AD···AD—H···A
C2—H2A···O1viii0.962.583.533 (4)171
Symmetry codes: (viii) −x−1, −y+1, −z.
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WN2286).
References
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
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  • Thiruvalluvar, A., Subramanyam, M., Butcher, R. J. & Mahalinga, M. (2007). Acta Cryst. E63, o4770.
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