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

Chakib, I.; Zerzouf, A.; Rodi, Y.K.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536811037652

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2700

https://doi.org/10.1107/S1600536811037652

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

Imane Chakib,^a Abdelfettah Zerzouf,^a Youssef Kandri Rodi,^b El Mokhtar Essassi ^a and Seik Weng Ng ^c,^d ^*

^aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, ^bLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, Université Sidi Mohamed Ben Abdallah, Fés, Morocco, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^dChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 14 September 2011; accepted 15 September 2011; online 30 September 2011)

The central five-membered ring of the title compound, C₁₈H₁₅N₃OS, is almost planar (r.m.s. deviation = 0.028 Å) and the benzothiazole fused-ring system is close to coplanar with this ring [dihedral angle = 6.1 (1)°]. The phenyl substituent is twisted by 62.5 (1)°.

Related literature

For the structure of the reactant 4-(2,3-dihydro-1,3-benzothiazol-2-ylidene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one, see: Chakibe et al. (2010 ).

Experimental

Crystal data

C₁₈H₁₅N₃OS
M_r = 321.39
Monoclinic, P 2₁ /c
a = 8.7428 (2) Å
b = 25.7551 (5) Å
c = 6.9660 (1) Å
β = 97.460 (1)°
V = 1555.27 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 293 K
0.50 × 0.10 × 0.10 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.900, T_max = 0.979
18953 measured reflections
3569 independent reflections
2418 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.131
S = 1.01
3569 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811037652/jh2331sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811037652/jh2331Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811037652/jh2331Isup3.cml

checkCIF report

Comment top

In the study, the tertiary nitrogen atom of the five-membered ring of 4-(2,3-dihydro-1,3-benzothiazol-2-ylidene)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one (Chakibe et al., 2010) is used to displace iodine from methyl iode to give the title compound; the carbon-carbon double-bond in the reactant is consequently converted to a double bond (Scheme I, Fig. 1). The central five-membered ring and the benzothiazolyl fused-ring is nearly co-planar (dihedral angle 6.1 (1) °). The phenyl substituent is twisted by 62.5 (1) ° with respect to the five-membered ring.

Related literature top

For the structure of the reactant, see: Chakibe et al. (2010).

Experimental top

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-butylammonium bromide (0.15 g, 1 mmol) and methyl iodide (7.1 g, 50 mmol). The mixture was stirred for 24 h. The solid material was removed b filtration and the solution was evaporated. The residue was washed with dichloromethane and hexane, and was recrystallized from ethanol to afford the title compound as colorless crystals.

Structure description top

For the structure of the reactant, see: Chakibe et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₈H₁₅N₃OS at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

4-(1,3-Benzothiazol-2-yl)-1,5-dimethyl-2-phenyl-1H-pyrazol- 3(2H)-one top

Crystal data top

C₁₈H₁₅N₃OS	F(000) = 672
M_r = 321.39	D_x = 1.373 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3894 reflections
a = 8.7428 (2) Å	θ = 2.5–24.6°
b = 25.7551 (5) Å	µ = 0.22 mm⁻¹
c = 6.9660 (1) Å	T = 293 K
β = 97.460 (1)°	Prism, colorless
V = 1555.27 (5) Å³	0.50 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	3569 independent reflections
Radiation source: fine-focus sealed tube	2418 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
φ and ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.900, T_max = 0.979	k = −29→33
18953 measured reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0644P)² + 0.296P] where P = (F_o² + 2F_c²)/3
3569 reflections	(Δ/σ)_max = 0.001
210 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₈H₁₅N₃OS	V = 1555.27 (5) Å³
M_r = 321.39	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.7428 (2) Å	µ = 0.22 mm⁻¹
b = 25.7551 (5) Å	T = 293 K
c = 6.9660 (1) Å	0.50 × 0.10 × 0.10 mm
β = 97.460 (1)°

Data collection top

Bruker APEXII diffractometer	3569 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2418 reflections with I > 2σ(I)
T_min = 0.900, T_max = 0.979	R_int = 0.053
18953 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.01	Δρ_max = 0.26 e Å⁻³
3569 reflections	Δρ_min = −0.27 e Å⁻³
210 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.92125 (7)	0.46686 (2)	0.19736 (8)	0.04602 (18)
N1	0.8107 (2)	0.43170 (7)	0.5013 (3)	0.0485 (5)
N2	0.6696 (2)	0.60559 (6)	0.3813 (2)	0.0450 (4)
N3	0.6087 (2)	0.58549 (6)	0.5419 (2)	0.0436 (4)
O1	0.80712 (19)	0.57089 (6)	0.1499 (2)	0.0555 (4)
C1	0.9552 (2)	0.40265 (8)	0.2603 (3)	0.0435 (5)
C2	1.0365 (3)	0.36554 (8)	0.1694 (3)	0.0531 (6)
H2	1.0832	0.3740	0.0609	0.064*
C3	1.0459 (3)	0.31630 (9)	0.2442 (4)	0.0611 (7)
H3	1.1003	0.2910	0.1862	0.073*
C4	0.9756 (3)	0.30371 (9)	0.4045 (4)	0.0682 (7)
H4	0.9818	0.2698	0.4510	0.082*
C5	0.8967 (3)	0.34025 (9)	0.4969 (4)	0.0657 (7)
H5	0.8506	0.3313	0.6053	0.079*
C6	0.8869 (2)	0.39090 (8)	0.4253 (3)	0.0462 (5)
C7	0.8201 (2)	0.47347 (7)	0.3978 (3)	0.0399 (5)
C8	0.7531 (2)	0.56620 (8)	0.3030 (3)	0.0417 (5)
C9	0.7516 (2)	0.52318 (7)	0.4329 (3)	0.0387 (5)
C10	0.6676 (2)	0.53751 (7)	0.5781 (3)	0.0398 (5)
C11	0.6421 (3)	0.50940 (9)	0.7570 (3)	0.0514 (6)
H11A	0.5334	0.5064	0.7630	0.077*
H11B	0.6897	0.5282	0.8679	0.077*
H11C	0.6868	0.4754	0.7559	0.077*
C12	0.5534 (3)	0.62109 (9)	0.6788 (3)	0.0527 (6)
H12A	0.5437	0.6031	0.7972	0.079*
H12B	0.4546	0.6346	0.6253	0.079*
H12C	0.6252	0.6492	0.7045	0.079*
C13	0.5892 (3)	0.64466 (7)	0.2625 (3)	0.0414 (5)
C14	0.4314 (3)	0.64253 (9)	0.2115 (3)	0.0532 (6)
H14	0.3732	0.6167	0.2606	0.064*
C15	0.3615 (3)	0.67960 (10)	0.0859 (4)	0.0657 (7)
H15	0.2553	0.6787	0.0497	0.079*
C16	0.4484 (4)	0.71801 (10)	0.0139 (4)	0.0673 (8)
H16	0.4007	0.7428	−0.0705	0.081*
C17	0.6046 (4)	0.71958 (9)	0.0666 (4)	0.0627 (7)
H17	0.6629	0.7454	0.0175	0.075*
C18	0.6759 (3)	0.68310 (8)	0.1916 (3)	0.0508 (5)
H18	0.7820	0.6844	0.2281	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0543 (3)	0.0407 (3)	0.0427 (3)	0.0044 (2)	0.0050 (2)	0.0038 (2)
N1	0.0525 (11)	0.0414 (10)	0.0524 (11)	0.0046 (8)	0.0100 (9)	0.0068 (8)
N2	0.0576 (11)	0.0379 (9)	0.0397 (9)	0.0063 (8)	0.0079 (8)	0.0048 (7)
N3	0.0568 (11)	0.0403 (10)	0.0334 (9)	0.0041 (8)	0.0047 (8)	−0.0002 (7)
O1	0.0732 (11)	0.0503 (9)	0.0456 (9)	0.0109 (8)	0.0180 (8)	0.0067 (7)
C1	0.0397 (11)	0.0404 (11)	0.0480 (12)	−0.0006 (9)	−0.0033 (9)	0.0008 (9)
C2	0.0500 (13)	0.0493 (13)	0.0590 (14)	0.0057 (11)	0.0036 (11)	−0.0051 (11)
C3	0.0572 (15)	0.0471 (14)	0.0778 (17)	0.0078 (11)	0.0044 (13)	−0.0065 (12)
C4	0.0668 (17)	0.0390 (13)	0.099 (2)	0.0085 (12)	0.0103 (15)	0.0110 (13)
C5	0.0698 (16)	0.0469 (14)	0.0841 (18)	0.0074 (12)	0.0240 (14)	0.0183 (13)
C6	0.0429 (12)	0.0386 (11)	0.0560 (13)	0.0005 (9)	0.0026 (10)	0.0061 (9)
C7	0.0398 (11)	0.0391 (11)	0.0383 (10)	−0.0017 (9)	−0.0043 (8)	0.0018 (8)
C8	0.0485 (12)	0.0376 (11)	0.0381 (11)	0.0028 (9)	0.0016 (9)	−0.0011 (8)
C9	0.0424 (11)	0.0360 (10)	0.0353 (10)	0.0003 (9)	−0.0036 (8)	−0.0004 (8)
C10	0.0433 (11)	0.0389 (11)	0.0342 (10)	−0.0014 (9)	−0.0067 (8)	−0.0005 (8)
C11	0.0613 (14)	0.0524 (13)	0.0392 (11)	0.0003 (11)	0.0020 (10)	0.0049 (10)
C12	0.0629 (15)	0.0518 (13)	0.0438 (12)	0.0052 (11)	0.0077 (11)	−0.0078 (10)
C13	0.0561 (13)	0.0316 (10)	0.0365 (10)	0.0055 (9)	0.0052 (9)	−0.0033 (8)
C14	0.0567 (14)	0.0439 (12)	0.0582 (14)	0.0007 (11)	0.0043 (11)	0.0035 (10)
C15	0.0643 (16)	0.0681 (17)	0.0617 (16)	0.0190 (13)	−0.0025 (13)	0.0022 (13)
C16	0.098 (2)	0.0560 (15)	0.0487 (14)	0.0268 (15)	0.0123 (14)	0.0137 (11)
C17	0.094 (2)	0.0384 (13)	0.0596 (15)	0.0055 (13)	0.0241 (14)	0.0075 (11)
C18	0.0626 (14)	0.0399 (12)	0.0506 (13)	−0.0025 (11)	0.0100 (11)	−0.0024 (10)

Geometric parameters (Å, º) top

S1—C1	1.727 (2)	C8—C9	1.432 (3)
S1—C7	1.755 (2)	C9—C10	1.376 (3)
N1—C7	1.304 (2)	C10—C11	1.483 (3)
N1—C6	1.386 (3)	C11—H11A	0.9600
N2—C8	1.401 (3)	C11—H11B	0.9600
N2—N3	1.399 (2)	C11—H11C	0.9600
N2—C13	1.428 (2)	C12—H12A	0.9600
N3—C10	1.350 (2)	C12—H12B	0.9600
N3—C12	1.451 (3)	C12—H12C	0.9600
O1—C8	1.227 (2)	C13—C18	1.377 (3)
C1—C2	1.392 (3)	C13—C14	1.381 (3)
C1—C6	1.395 (3)	C14—C15	1.382 (3)
C2—C3	1.369 (3)	C14—H14	0.9300
C2—H2	0.9300	C15—C16	1.381 (4)
C3—C4	1.382 (4)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.368 (4)
C4—C5	1.375 (4)	C16—H16	0.9300
C4—H4	0.9300	C17—C18	1.374 (3)
C5—C6	1.395 (3)	C17—H17	0.9300
C5—H5	0.9300	C18—H18	0.9300
C7—C9	1.448 (3)

C1—S1—C7	88.78 (10)	C8—C9—C7	122.65 (19)
C7—N1—C6	110.27 (18)	N3—C10—C9	109.58 (17)
C8—N2—N3	108.35 (15)	N3—C10—C11	120.60 (19)
C8—N2—C13	121.79 (16)	C9—C10—C11	129.77 (19)
N3—N2—C13	120.94 (17)	C10—C11—H11A	109.5
C10—N3—N2	108.24 (16)	C10—C11—H11B	109.5
C10—N3—C12	127.40 (17)	H11A—C11—H11B	109.5
N2—N3—C12	119.07 (16)	C10—C11—H11C	109.5
C2—C1—C6	121.6 (2)	H11A—C11—H11C	109.5
C2—C1—S1	128.56 (18)	H11B—C11—H11C	109.5
C6—C1—S1	109.83 (16)	N3—C12—H12A	109.5
C3—C2—C1	118.1 (2)	N3—C12—H12B	109.5
C3—C2—H2	120.9	H12A—C12—H12B	109.5
C1—C2—H2	120.9	N3—C12—H12C	109.5
C2—C3—C4	120.9 (2)	H12A—C12—H12C	109.5
C2—C3—H3	119.5	H12B—C12—H12C	109.5
C4—C3—H3	119.5	C18—C13—C14	121.0 (2)
C5—C4—C3	121.4 (2)	C18—C13—N2	117.5 (2)
C5—C4—H4	119.3	C14—C13—N2	121.43 (19)
C3—C4—H4	119.3	C15—C14—C13	118.7 (2)
C4—C5—C6	119.0 (2)	C15—C14—H14	120.7
C4—C5—H5	120.5	C13—C14—H14	120.7
C6—C5—H5	120.5	C14—C15—C16	120.4 (3)
N1—C6—C5	125.6 (2)	C14—C15—H15	119.8
N1—C6—C1	115.37 (18)	C16—C15—H15	119.8
C5—C6—C1	119.0 (2)	C17—C16—C15	120.1 (2)
N1—C7—C9	125.38 (19)	C17—C16—H16	120.0
N1—C7—S1	115.75 (15)	C15—C16—H16	120.0
C9—C7—S1	118.85 (15)	C16—C17—C18	120.3 (2)
O1—C8—N2	123.08 (18)	C16—C17—H17	119.9
O1—C8—C9	131.43 (19)	C18—C17—H17	119.9
N2—C8—C9	105.45 (17)	C17—C18—C13	119.6 (2)
C10—C9—C8	107.86 (17)	C17—C18—H18	120.2
C10—C9—C7	129.34 (18)	C13—C18—H18	120.2

C8—N2—N3—C10	7.4 (2)	N2—C8—C9—C10	1.0 (2)
C13—N2—N3—C10	155.18 (17)	O1—C8—C9—C7	−0.5 (4)
C8—N2—N3—C12	163.59 (18)	N2—C8—C9—C7	176.98 (18)
C13—N2—N3—C12	−48.6 (3)	N1—C7—C9—C10	1.4 (3)
C7—S1—C1—C2	−179.4 (2)	S1—C7—C9—C10	179.71 (16)
C7—S1—C1—C6	0.61 (15)	N1—C7—C9—C8	−173.65 (19)
C6—C1—C2—C3	1.2 (3)	S1—C7—C9—C8	4.7 (3)
S1—C1—C2—C3	−178.77 (17)	N2—N3—C10—C9	−6.8 (2)
C1—C2—C3—C4	0.4 (4)	C12—N3—C10—C9	−160.4 (2)
C2—C3—C4—C5	−1.3 (4)	N2—N3—C10—C11	171.05 (18)
C3—C4—C5—C6	0.5 (4)	C12—N3—C10—C11	17.4 (3)
C7—N1—C6—C5	−178.3 (2)	C8—C9—C10—N3	3.6 (2)
C7—N1—C6—C1	0.0 (3)	C7—C9—C10—N3	−172.02 (19)
C4—C5—C6—N1	179.4 (2)	C8—C9—C10—C11	−174.0 (2)
C4—C5—C6—C1	1.1 (4)	C7—C9—C10—C11	10.4 (4)
C2—C1—C6—N1	179.51 (19)	C8—N2—C13—C18	−74.5 (2)
S1—C1—C6—N1	−0.5 (2)	N3—N2—C13—C18	142.02 (19)
C2—C1—C6—C5	−2.0 (3)	C8—N2—C13—C14	101.9 (2)
S1—C1—C6—C5	177.98 (18)	N3—N2—C13—C14	−41.5 (3)
C6—N1—C7—C9	178.88 (19)	C18—C13—C14—C15	0.5 (3)
C6—N1—C7—S1	0.5 (2)	N2—C13—C14—C15	−175.8 (2)
C1—S1—C7—N1	−0.67 (16)	C13—C14—C15—C16	−0.2 (4)
C1—S1—C7—C9	−179.16 (17)	C14—C15—C16—C17	0.0 (4)
N3—N2—C8—O1	172.67 (19)	C15—C16—C17—C18	−0.2 (4)
C13—N2—C8—O1	25.2 (3)	C16—C17—C18—C13	0.5 (3)
N3—N2—C8—C9	−5.1 (2)	C14—C13—C18—C17	−0.7 (3)
C13—N2—C8—C9	−152.51 (18)	N2—C13—C18—C17	175.78 (19)
O1—C8—C9—C10	−176.5 (2)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₅N₃OS
M_r	321.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.7428 (2), 25.7551 (5), 6.9660 (1)
β (°)	97.460 (1)
V (Å³)	1555.27 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.50 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.900, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	18953, 3569, 2418
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.131, 1.01
No. of reflections	3569
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.27

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

The authors thank Université Sidi Mohamed Ben Abdallah, Université Mohammed V-Agdal and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chakibe, I., Zerzouf, A., Essassi, E. M., Reichelt, M. & Reuter, H. (2010). Acta Cryst. E66, o1096. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar