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Acta Cryst. (2008). E64, o2160    [ doi:10.1107/S1600536808033837 ]

1-[3-(2,4-Dichloro-5-fluorophenyl)-5-(3-methyl-2-thienyl)-4,5-dihydro-1H-pyrazol-1-yl]ethanone

N. Anuradha, A. Thiruvalluvar, M. Mahalinga and R. J. Butcher

Abstract top

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.

Comment top

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.

Related literature top

For a related crystal structure, see: Thiruvalluvar et al. (2007).

Experimental top

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 top

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.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 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.
[Figure 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.
1-[3-(2,4-Dichloro-5-fluorophenyl)-5-(3-methyl-2-thienyl)-4,5-dihydro-1H- pyrazol-1-yl]ethanone top
Crystal data top
C16H13Cl2FN2OSZ = 2
Mr = 371.25F(000) = 380
Triclinic, P1Dx = 1.478 Mg m−3
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 mm−1
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 top
Oxford Diffraction R Gemini
diffractometer		5445 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°
φ 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 top
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 = 1.12 w = 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 Å−3
0 restraintsΔρmin = −0.39 e Å−3
Crystal data top
C16H13Cl2FN2OSγ = 101.003 (5)°
Mr = 371.25V = 833.99 (10) Å3
Triclinic, P1Z = 2
a = 7.2240 (5) ÅMo Kα radiation
b = 8.8642 (4) ŵ = 0.53 mm−1
c = 14.0518 (9) ÅT = 295 K
α = 100.794 (5)°0.52 × 0.43 × 0.35 mm
β = 103.307 (6)°
Data collection top
Oxford Diffraction R Gemini
diffractometer		5445 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2008)		3028 reflections with I > 2σ(I)
Tmin = 0.786, Tmax = 1.000Rint = 0.020
12358 measured reflectionsθmax = 32.5°
Refinement top
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.179Δρmax = 0.32 e Å−3
S = 1.12Δρmin = −0.39 e Å−3
5445 reflectionsAbsolute structure: ?
210 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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) top
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) top
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, °) top
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, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O1viii0.962.583.533 (4)171
Symmetry codes: (viii) −x−1, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O1i0.962.583.533 (4)171
Symmetry codes: (i) −x−1, −y+1, −z.
Acknowledgements top

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.

references
References top

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Thiruvalluvar, A., Subramanyam, M., Butcher, R. J. & Mahalinga, M. (2007). Acta Cryst. E63, o4770.