Literature DB >> 21581020

1-[3-(2,4-Dichloro-5-fluoro-phen-yl)-5-(3-methyl-2-thien-yl)-4,5-dihydro-1H-pyrazol-1-yl]ethanone.

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

Abstract

In the title mol-ecule, C(16)H(13)Cl(2)FN(2)OS, the dihedral angle between the thio-phene 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 thio-phene 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 inter-molecular C-H⋯O hydrogen bonds. A short inter-molecular Cl⋯S contact of 3.4250 (13) Å is also found.

Entities:  

Year:  2008        PMID： 21581020      PMCID： PMC2959565          DOI： 10.1107/S1600536808033837

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

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

Experimental

Crystal data

C16H13Cl2FN2OS M = 371.25 Triclinic, 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 ▶) 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 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; 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 ▶). 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
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
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°
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 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 Å−3
0 restraintsΔρmin = −0.39 e Å−3
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.
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*
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)
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)
D—H···AD—HH···AD···AD—H···A
C2—H2A···O1viii0.962.583.533 (4)171
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯AD—HH⋯AD⋯AD—H⋯A
C2—H2A⋯O1i0.962.583.533 (4)171

Symmetry code: (i) .

  1 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290
  1 in total
  2 in total

1.  1-[3,5-Bis(4-fluoro-phen-yl)-4,5-dihydro-1H-pyrazol-1-yl]ethanone.

Authors:  Hoong-Kun Fun; Madhukar Hemamalini; S Samshuddin; B Narayana; H S Yathirajan
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2010-02-10

2.  1-[3,5-Bis(4-chloro-phen-yl)-4,5-dihydro-1H-pyrazol-1-yl]ethanone.

Authors:  Jerry P Jasinski; Albert E Pek; S Samshuddin; B Narayana; H S Yathirajan
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2010-07-07
  2 in total

北京卡尤迪生物科技股份有限公司 © 2022-2023.