(E)-4-(2,3-Dihydro-1,3-benzothia­zol-2-yl­idene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Imane Chakibe; Abdelfettah Zerzouf; El Mokhtar Essassi; Martin Reichelt; Hans Reuter

doi:10.1107/S1600536810013176

. 2010 Apr 17;66(Pt 5):o1096. doi: 10.1107/S1600536810013176

(E)-4-(2,3-Dihydro-1,3-benzothiazol-2-ylidene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one

Imane Chakibe ^a, Abdelfettah Zerzouf ^b, El Mokhtar Essassi ^c, Martin Reichelt ^d, Hans Reuter ^d,^*

PMCID: PMC2979087 PMID: 21579149

Abstract

In the title compound, C₁₇H₁₃N₃OS, the dihedral angle between the ring systems is 2.22 (5)°. The N—H grouping participates in both intra- and intermolecular N—H⋯O hydrogen bonds, the latter leading to dimers related by a twofold rotation axis.

Related literature

For related structures, see: Teo et al. (1993 ▶); Chen (1994 ▶); Sawusch & Schilde (1999 ▶); Chu et al. (2003 ▶); Liu et al. (2004 ▶). For related literature, see: Harnden et al. (1978 ▶); Hatheway et al. (1978 ▶); Londershausen (1996 ▶); Tewari & Mishra (2001 ▶). graphic file with name e-66-o1096-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₃N₃OS
M _r = 307.36
Monoclinic,
a = 27.0144 (8) Å
b = 7.4021 (2) Å
c = 14.0523 (4) Å
β = 97.466 (1)°
V = 2786.12 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.40 × 0.28 × 0.20 mm

Data collection

Bruker APEXII with a CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.875, T _max = 0.956
57380 measured reflections
3359 independent reflections
2928 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.082
S = 1.05
3359 reflections
203 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810013176/fk2016sup1.cif

e-66-o1096-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013176/fk2016Isup2.hkl

e-66-o1096-Isup2.hkl^{(164.9KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O15	0.88	2.24	2.8483 (14)	126
N3—H3⋯O15ⁱ	0.88	2.22	2.9161 (13)	136

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the Deutsche Forschungsgemeinschaft and the Government of Lower Saxony for their financial support in the acquisition of the diffractometer.

supplementary crystallographic information

Comment

The chemistry of pyrazole derivatives has been the subject of much interest due to their importance for various applications and their widespread potential and proven biological and pharmacological activities such as anti-inflammatory (Tewari et al., 2001), antimicrobial, antiviral (Harnden et al., 1978), anti-tumor (Hatheway et al., 1978), anti-fungal and pesticidal substances (Londershausen et al., 1996).

The new pyrazole derivative (E)-4-(benzo[d]thiazol-2-(3H)-ylidene)-3-methyl-1- phenyl-1H-pyrazol-5(4H)-one, 3, was synthesised according to reaction scheme 1. The solid state structure of 3 (Fig. 1) shows the typical structural features of its three subunits: a phenyl rest, a pyrazole derivative and a benzothiazole-like fragment.

In the pyrazol moiety the shortening of the bond between N12 and C13 [1.307 (2) Å] corresponds to a double bond in accordance with the formulation of the double bond in scheme 1.

All of the three subunits are for themselves planar, deviations from the least-square planes are small. Within the benzo[d]thiazole the greatest deviations result from the fact that the phenyl ring is planar whereas the remaining atoms of the thiazole ring are out of this plane with a maximum at C2 [-0.055 (2) Å]. Moreover, the complete molecule adopts are slightly curved conformation (Fig. 2). In the case of the 1,3-benzothiazole-pyrazole bond planarity should be result from the double bond [d(C—C) = 1.388 (2) Å] between the two subunits. Nevertheless, the interplanar dihedral angle between both ring systems is 2.22 (5)°. Between the pyrazole and the phenyl fragment the carbon-carbon single bond is shortened [d(C—C) = 1.416 (2) Å] but even longer than a double bond. In this case, the interplanar dihedral angle between both fragments is 7.16 (6)°. Similar values between these two subunits were obsereved earlier (Liu et al. 2004).

In the solid state, 3 forms dimers (Fig. 3) by bifurcated hydrogen bonds between the NH-group [N3] of the 1,3-benzothiazole-rest and O15 of a neighbouring molecule, both related by a twofold rotation axis. The second part of the bifurcated hydrogen bond system combines the NH-group with O15 within the same molecule.

Experimental

1.98 g (0.1 mol) (E)-3-methyl-4-(4-methyl-1-phenylpyrano[2,3-c]pyrazol-6(1H)-ylidene)-1-phenyl-1H-pyrazol-5(4H)-one, 2, were refluxed for 72 h with 2.136 ml (0.02 mol) 2-aminobenzenethiol, 1, in 50 ml n-butanol. On cooling the product forms transparent colourless crystals, which were filtered off in a yield of 50%. A suitable single crystal was selected under a polarization microsope and mounted on a 50 µm MicroMesh MiTeGen Micromount^TMusing FROMBLIN Y perfluoropolyether (LVAC 16/6, Aldrich).