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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2843.
Published online 2010 October 20. doi:  10.1107/S1600536810040328
PMCID: PMC3008972

4-(1,3-Benzothia­zol-2-yl)-5-methyl-2-phenyl-1-propynyl-1H-pyrazol-3(2H)-one

Abstract

The title compound, C20H15N3OS, is a 1H-pyrazol-3(2H)-one having aromatic 4-(1,3-benzothia­zol-2-yl) and 2-phenyl substit­uents. The five-membered ring and the fused-ring system are close to planar, the r.m.s. deviations being 0.025 and 0.005 Å, respectively. The five-membered ring is aligned at 67.5 (1)° with respect to the phenyl ring and at 4.7 (1)° with respect to the fused-ring system. In the crystal, adjacent mol­ecules are linked through the acetyl­enic H atom by a C—H(...)O hydrogen bond into C(8) chains propagating in [010].

Related literature

For the structure of a similar compound, 4-(benzo[d]thia­zol-2-yl)-2-allyl-3-methyl-1-phenyl-1,2-dihydro­pyrazol-5-one, see: Chakibe et al. (2010 [triangle]). For the structure of a related compound, (E)-4-(2,3-dihydro-1,3-benzothia­zol-2-yl­idene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, see: Chakib et al. (2010 [triangle]).

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Object name is e-66-o2843-scheme1.jpg

Experimental

Crystal data

  • C20H15N3OS
  • M r = 345.41
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2843-efi1.jpg
  • a = 4.8221 (1) Å
  • b = 9.3698 (2) Å
  • c = 37.6990 (9) Å
  • V = 1703.32 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.20 mm−1
  • T = 293 K
  • 0.40 × 0.20 × 0.20 mm

Data collection

  • Bruker X8 APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.923, T max = 0.961
  • 10502 measured reflections
  • 3699 independent reflections
  • 3008 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.105
  • S = 0.99
  • 3699 reflections
  • 227 parameters
  • H-atom parameters constrained
  • Δρmax = 0.20 e Å−3
  • Δρmin = −0.19 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1483 Friedel pairs
  • Flack parameter: 0.00 (9)

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810040328/xu5048sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040328/xu5048Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank Université Mohammed V-Agdal and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

(E)-4-(2,3-Dihydro-1,3-benzothiazol-2-ylidene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one is an amine that can under a nucleophilic substitution with organo bromides to form 2-substituted derivatives if tetra-n-butyl ammonium bromide is used as catalyst. In this study, the compound is reacted with propargyl bromide to yield the title compound (Scheme I, Fig. 1).

Experimental

To a solution of (E)-4-(2,3-dihydro-1,3-benzothiazol-2-ylidene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (1 g, 3.25 mmol) in DMF (50 ml), was added sodium carbonate (2.5 g, 23 mmol), tetra-n-butyl ammonium bromide (0.15 g, 1 mmol) and propargyl bromide (5.5 g, 46 mmol). The mixture was stirred for 24 h at room temperature. The solid material was removed by filtration and the solution was evaporated under reduced. The residue was washed with dichloromethane and hexane, and the recrystallized from ethanol to afford the title compound as yellow crystals.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5Ueq(C).

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C20H15N3OS at the 50% probability level; hydrogen atoms are drawn as arbitrary radius.
Fig. 2.
Hydrogen-bonded chain structure.

Crystal data

C20H15N3OSF(000) = 720
Mr = 345.41Dx = 1.347 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2503 reflections
a = 4.8221 (1) Åθ = 2.4–22.9°
b = 9.3698 (2) ŵ = 0.20 mm1
c = 37.6990 (9) ÅT = 293 K
V = 1703.32 (6) Å3Prism, yellow
Z = 40.40 × 0.20 × 0.20 mm

Data collection

Bruker X8 APEXII diffractometer3699 independent reflections
Radiation source: fine-focus sealed tube3008 reflections with I > 2σ(I)
graphiteRint = 0.033
[var phi] and ω scansθmax = 27.1°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −5→6
Tmin = 0.923, Tmax = 0.961k = −11→11
10502 measured reflectionsl = −47→46

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.105w = 1/[σ2(Fo2) + (0.0613P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
3699 reflectionsΔρmax = 0.20 e Å3
227 parametersΔρmin = −0.19 e Å3
0 restraintsAbsolute structure: Flack (1983), 1483 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.00 (9)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S10.55911 (13)0.45298 (6)0.105599 (16)0.04655 (17)
O10.9129 (4)0.52382 (15)0.16533 (4)0.0487 (4)
N10.5947 (4)0.6723 (2)0.06358 (5)0.0445 (4)
N21.1641 (4)0.85264 (18)0.14034 (5)0.0422 (4)
N31.1570 (4)0.73580 (18)0.16370 (5)0.0408 (4)
C10.3603 (5)0.4536 (3)0.06743 (6)0.0469 (5)
C20.1735 (6)0.3514 (3)0.05524 (7)0.0599 (7)
H20.14220.26800.06800.072*
C30.0366 (6)0.3767 (3)0.02398 (8)0.0681 (8)
H3−0.08940.30970.01550.082*
C40.0833 (6)0.4998 (3)0.00504 (8)0.0683 (8)
H4−0.01210.5142−0.01610.082*
C50.2662 (5)0.6015 (3)0.01643 (7)0.0593 (7)
H50.29610.68410.00330.071*
C60.4073 (5)0.5783 (3)0.04845 (6)0.0446 (5)
C70.6919 (5)0.6195 (2)0.09303 (6)0.0376 (5)
C80.9769 (5)0.6346 (2)0.14978 (5)0.0386 (5)
C90.8913 (4)0.6897 (2)0.11590 (5)0.0351 (4)
C101.0182 (4)0.8196 (2)0.11109 (5)0.0386 (5)
C111.0201 (6)0.9159 (3)0.07987 (6)0.0558 (7)
H11A0.98301.01190.08740.084*
H11B0.88000.88610.06340.084*
H11C1.19850.91200.06860.084*
C121.3789 (5)0.9610 (2)0.14413 (7)0.0479 (6)
H12A1.49650.93710.16410.057*
H12B1.49340.96200.12300.057*
C131.2600 (5)1.1024 (3)0.14956 (6)0.0494 (6)
C141.1643 (7)1.2142 (3)0.15376 (8)0.0657 (8)
H141.08731.30420.15710.079*
C151.2100 (5)0.7561 (2)0.20074 (5)0.0383 (5)
C161.0709 (5)0.8595 (3)0.21937 (7)0.0534 (6)
H160.94440.91890.20800.064*
C171.1218 (6)0.8741 (3)0.25519 (7)0.0625 (7)
H171.02930.94400.26810.075*
C181.3064 (6)0.7867 (3)0.27184 (7)0.0588 (7)
H181.33890.79730.29600.071*
C191.4434 (6)0.6842 (3)0.25322 (7)0.0629 (7)
H191.56930.62480.26470.075*
C201.3951 (5)0.6682 (3)0.21707 (6)0.0505 (6)
H201.48800.59830.20420.061*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0594 (3)0.0375 (3)0.0427 (3)−0.0076 (3)0.0002 (3)0.0022 (2)
O10.0764 (10)0.0299 (8)0.0397 (9)−0.0053 (8)−0.0008 (9)0.0053 (6)
N10.0509 (11)0.0449 (11)0.0376 (10)−0.0009 (9)0.0005 (9)0.0036 (8)
N20.0573 (11)0.0309 (9)0.0386 (11)−0.0056 (8)0.0001 (9)0.0042 (8)
N30.0598 (12)0.0303 (9)0.0323 (10)−0.0002 (8)−0.0029 (9)0.0021 (8)
C10.0480 (12)0.0497 (13)0.0431 (13)0.0012 (11)0.0078 (10)−0.0093 (11)
C20.0620 (15)0.0589 (17)0.0587 (17)−0.0136 (13)0.0045 (13)−0.0111 (13)
C30.0521 (14)0.086 (2)0.0662 (19)−0.0125 (15)0.0019 (14)−0.0292 (17)
C40.0551 (15)0.096 (2)0.0535 (17)0.0027 (16)−0.0097 (13)−0.0122 (15)
C50.0586 (15)0.0776 (19)0.0418 (15)−0.0006 (14)−0.0034 (12)0.0016 (13)
C60.0435 (12)0.0544 (14)0.0358 (12)0.0030 (11)0.0021 (10)−0.0053 (10)
C70.0442 (11)0.0346 (11)0.0340 (12)0.0014 (9)0.0085 (9)−0.0004 (9)
C80.0528 (13)0.0297 (10)0.0334 (12)0.0042 (9)0.0042 (9)−0.0043 (8)
C90.0456 (11)0.0301 (10)0.0297 (10)0.0026 (9)0.0057 (9)0.0008 (8)
C100.0488 (12)0.0333 (10)0.0336 (12)0.0023 (8)0.0052 (9)0.0002 (9)
C110.0780 (17)0.0472 (14)0.0422 (14)−0.0119 (12)0.0012 (12)0.0132 (10)
C120.0470 (12)0.0391 (12)0.0577 (15)−0.0027 (10)0.0044 (11)0.0016 (11)
C130.0636 (15)0.0378 (13)0.0467 (15)−0.0098 (12)0.0002 (12)0.0017 (10)
C140.093 (2)0.0388 (14)0.0652 (18)0.0028 (14)0.0063 (16)0.0001 (12)
C150.0451 (12)0.0360 (12)0.0339 (12)−0.0026 (9)−0.0016 (9)−0.0021 (9)
C160.0570 (13)0.0545 (15)0.0487 (14)0.0157 (12)−0.0105 (12)−0.0128 (11)
C170.0676 (16)0.0679 (18)0.0519 (16)0.0054 (14)−0.0002 (14)−0.0231 (13)
C180.0733 (17)0.0678 (18)0.0353 (14)−0.0125 (15)−0.0049 (13)−0.0038 (12)
C190.0728 (17)0.0678 (17)0.0479 (15)0.0121 (15)−0.0133 (14)0.0063 (13)
C200.0628 (15)0.0459 (13)0.0428 (13)0.0117 (12)−0.0012 (12)−0.0030 (11)

Geometric parameters (Å, °)

S1—C11.729 (2)C9—C101.374 (3)
S1—C71.752 (2)C10—C111.483 (3)
O1—C81.232 (2)C11—H11A0.9600
N1—C71.303 (3)C11—H11B0.9600
N1—C61.385 (3)C11—H11C0.9600
N2—C101.344 (3)C12—C131.458 (3)
N2—N31.405 (2)C12—H12A0.9700
N2—C121.458 (3)C12—H12B0.9700
N3—C81.389 (3)C13—C141.156 (4)
N3—C151.433 (3)C14—H140.9300
C1—C61.389 (3)C15—C201.362 (3)
C1—C21.393 (3)C15—C161.372 (3)
C2—C31.371 (4)C16—C171.379 (3)
C2—H20.9300C16—H160.9300
C3—C41.375 (4)C17—C181.362 (4)
C3—H30.9300C17—H170.9300
C4—C51.368 (4)C18—C191.361 (4)
C4—H40.9300C18—H180.9300
C5—C61.403 (3)C19—C201.391 (3)
C5—H50.9300C19—H190.9300
C7—C91.449 (3)C20—H200.9300
C8—C91.438 (3)
C1—S1—C788.55 (12)N2—C10—C9109.20 (18)
C7—N1—C6110.14 (19)N2—C10—C11120.51 (19)
C10—N2—N3108.77 (17)C9—C10—C11130.3 (2)
C10—N2—C12127.79 (18)C10—C11—H11A109.5
N3—N2—C12119.92 (19)C10—C11—H11B109.5
C8—N3—N2108.09 (17)H11A—C11—H11B109.5
C8—N3—C15124.80 (18)C10—C11—H11C109.5
N2—N3—C15120.19 (17)H11A—C11—H11C109.5
C6—C1—C2120.9 (2)H11B—C11—H11C109.5
C6—C1—S1109.94 (18)C13—C12—N2111.6 (2)
C2—C1—S1129.1 (2)C13—C12—H12A109.3
C3—C2—C1118.5 (3)N2—C12—H12A109.3
C3—C2—H2120.8C13—C12—H12B109.3
C1—C2—H2120.8N2—C12—H12B109.3
C2—C3—C4120.8 (3)H12A—C12—H12B108.0
C2—C3—H3119.6C14—C13—C12179.6 (3)
C4—C3—H3119.6C13—C14—H14180.0
C5—C4—C3121.9 (3)C20—C15—C16121.1 (2)
C5—C4—H4119.1C20—C15—N3118.5 (2)
C3—C4—H4119.1C16—C15—N3120.4 (2)
C4—C5—C6118.3 (3)C15—C16—C17118.9 (2)
C4—C5—H5120.8C15—C16—H16120.5
C6—C5—H5120.8C17—C16—H16120.5
N1—C6—C1115.4 (2)C18—C17—C16120.5 (3)
N1—C6—C5124.9 (2)C18—C17—H17119.7
C1—C6—C5119.7 (2)C16—C17—H17119.7
N1—C7—C9125.0 (2)C19—C18—C17120.2 (2)
N1—C7—S1115.93 (17)C19—C18—H18119.9
C9—C7—S1119.08 (16)C17—C18—H18119.9
O1—C8—N3123.5 (2)C18—C19—C20120.0 (3)
O1—C8—C9130.8 (2)C18—C19—H19120.0
N3—C8—C9105.66 (18)C20—C19—H19120.0
C10—C9—C8107.89 (19)C15—C20—C19119.2 (2)
C10—C9—C7128.25 (19)C15—C20—H20120.4
C8—C9—C7123.76 (19)C19—C20—H20120.4
C10—N2—N3—C8−6.4 (2)O1—C8—C9—C72.1 (4)
C12—N2—N3—C8−166.84 (19)N3—C8—C9—C7−177.20 (19)
C10—N2—N3—C15−158.63 (19)N1—C7—C9—C10−1.5 (4)
C12—N2—N3—C1541.0 (3)S1—C7—C9—C10−179.60 (17)
C7—S1—C1—C6−0.38 (17)N1—C7—C9—C8174.4 (2)
C7—S1—C1—C2−179.8 (2)S1—C7—C9—C8−3.7 (3)
C6—C1—C2—C30.0 (4)N3—N2—C10—C96.0 (2)
S1—C1—C2—C3179.4 (2)C12—N2—C10—C9164.5 (2)
C1—C2—C3—C40.2 (4)N3—N2—C10—C11−172.1 (2)
C2—C3—C4—C5−0.1 (4)C12—N2—C10—C11−13.7 (3)
C3—C4—C5—C6−0.3 (4)C8—C9—C10—N2−3.4 (2)
C7—N1—C6—C11.1 (3)C7—C9—C10—N2173.0 (2)
C7—N1—C6—C5−179.4 (2)C8—C9—C10—C11174.5 (2)
C2—C1—C6—N1179.1 (2)C7—C9—C10—C11−9.1 (4)
S1—C1—C6—N1−0.3 (2)C10—N2—C12—C1381.7 (3)
C2—C1—C6—C5−0.4 (3)N3—N2—C12—C13−122.0 (2)
S1—C1—C6—C5−179.83 (18)C8—N3—C15—C2081.6 (3)
C4—C5—C6—N1−178.9 (2)N2—N3—C15—C20−131.0 (2)
C4—C5—C6—C10.5 (4)C8—N3—C15—C16−96.6 (3)
C6—N1—C7—C9−179.6 (2)N2—N3—C15—C1650.7 (3)
C6—N1—C7—S1−1.4 (2)C20—C15—C16—C170.2 (4)
C1—S1—C7—N11.08 (18)N3—C15—C16—C17178.4 (2)
C1—S1—C7—C9179.36 (17)C15—C16—C17—C18−0.3 (4)
N2—N3—C8—O1−175.2 (2)C16—C17—C18—C190.1 (4)
C15—N3—C8—O1−24.6 (3)C17—C18—C19—C200.0 (4)
N2—N3—C8—C94.2 (2)C16—C15—C20—C19−0.1 (4)
C15—N3—C8—C9154.8 (2)N3—C15—C20—C19−178.3 (2)
O1—C8—C9—C10178.7 (2)C18—C19—C20—C150.0 (4)
N3—C8—C9—C10−0.6 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C14—H14···O1i0.932.243.174 (3)179

Symmetry codes: (i) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5048).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chakib, I., Zerzouf, A., Zouihri, H., Essassi, E. M. & Ng, S. W. (2010). Acta Cryst E66, o2842. [PMC free article] [PubMed]
  • Chakibe, I., Zerzouf, A., Essassi, E. M., Reichelt, M. & Reuter, H. (2010). Acta Cryst. E66, o1096. [PMC free article] [PubMed]
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

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