(E)-4-(4-Chloro­phenyl)-N-(5-methyl-1,3-benzo­dioxol-5-yl­methylene)-5-(1H-1,2,4-triazol-1-yl)-1,3-thia­zol-2-amine

Shao, L.; Zhang, Q.; Zhou, X.; Fang, J.-X.

doi:10.1107/S1600536805042212

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(E)-4-(4-Chlorophenyl)-N-(5-methyl-1,3-benzodioxol-5-ylmethylene)-5-(1H-1,2,4-triazol-1-yl)-1,3-thiazol-2-amine

L. Shao, Q. Zhang, X. Zhou and J.-X. Fang

The title compound, C₁₉H₁₂ClN₅O₂S, has been synthesized as a potential fungicidal agent. The dihedral angle between the thiazole and triazole rings is 38.5 (1)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805042212/dn6288sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805042212/dn6288Isup2.hkl Contains datablock I

CCDC reference: 296559

checkCIF report

Key indicators

Single-crystal X-ray study
T = 294 K
Mean (C-C) = 0.004 Å
R factor = 0.045
wR factor = 0.126
Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O1      ..       3.26 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Thiazole derivatives are reported to exhibit diverse biological activities, such as antituberculous, bacteriostatic and fungistatic activities (Smia et al., 2000). In search of novel thiazole compounds with potent fungicidal activities, we have sought to synthesize such 2-aminothiazole compounds containing 1H-1,2,4-triazole units. We report here the crystal structure of the title compound, (I).

The molecular structure of (I) contains four planar subunits, namely a thiazole ring, a triazole ring, a 4-chlorophenyl ring and a methylbenzo[1,2-d]-1,3-dioxolyl ring. The methylbenzo[1,2-d]-1,3-dioxolyl and thiazole rings are nearly planar, with a dihedral angle between them of 3.0 (1)°, whereas the triazole and 4-chlorophenyl rings are twisted with respect to the thiazole by 38.5 (1) and 36.0 (1)°, respectively.

The occurrence of weak C—H···O interactions (Table 1) results in the formation of pseudo-dimers arranged around an inversion centre.

Experimental top

2-Amino-4-(4-chlorophenyl)-5-(1H-1,2,4-triazol-1-yl)-1,3-thiazole (0.42 g, 1.5 mmol) and heliotropin (0.22 g, 1.5 mmol) were mixed in benzene (20 ml). Three drops of piperidine were added to the mixed solution. The solution was then heated and refluxed in a 50 ml flask equipped with a Dean–Stark trap condenser until no water appeared (5 h). Concentration of the reaction solution and chromatography on a silica-gel column using ethyl acetate–petroleum ether (1:3) as eluent gave the title compound (0.51 g, yield 83.2%). Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation from ethanol.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. A molecular view of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view showing the formation of pseudo-dimers through weak C—H···O interactions (dashed lines). H atoms not involved in hydrogen bonds have been omitted for clarity.

(E)-4-(4-Chlorophenyl)-N-(5-methyl-1,3-benzodioxol-5-ylmethylene)- 5-(1H-1,2,4-triazol-1-yl)-1,3-thiazol-2-amine top

Crystal data top

C₁₉H₁₂ClN₅O₂S	Z = 2
M_r = 409.85	F(000) = 420
Triclinic, P1	D_x = 1.512 Mg m⁻³
Hall symbol: -P1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8260 (19) Å	Cell parameters from 1873 reflections
b = 8.929 (2) Å	θ = 2.9–26.3°
c = 14.221 (3) Å	µ = 0.36 mm⁻¹
α = 94.871 (4)°	T = 294 K
β = 92.332 (4)°	Block, yellow
γ = 114.170 (4)°	0.26 × 0.20 × 0.16 mm
V = 900.2 (4) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3160 independent reflections
Radiation source: fine-focus sealed tube	2302 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.910, T_max = 0.945	k = −10→9
4582 measured reflections	l = −15→16

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0622P)² + 0.3304P] where P = (F_o² + 2F_c²)/3
3160 reflections	(Δ/σ)_max = 0.001
253 parameters	Δρ_max = 0.32 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

C₁₉H₁₂ClN₅O₂S	γ = 114.170 (4)°
M_r = 409.85	V = 900.2 (4) Å³
Triclinic, P1	Z = 2
a = 7.8260 (19) Å	Mo Kα radiation
b = 8.929 (2) Å	µ = 0.36 mm⁻¹
c = 14.221 (3) Å	T = 294 K
α = 94.871 (4)°	0.26 × 0.20 × 0.16 mm
β = 92.332 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3160 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2302 reflections with I > 2σ(I)
T_min = 0.910, T_max = 0.945	R_int = 0.029
4582 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.01	Δρ_max = 0.32 e Å⁻³
3160 reflections	Δρ_min = −0.41 e Å⁻³
253 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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 > σ(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

	x	y	z	U_iso*/U_eq
S1	1.26020 (9)	0.46507 (8)	0.50351 (5)	0.0461 (2)
Cl1	0.66432 (13)	0.29773 (17)	−0.03482 (6)	0.1048 (4)
O1	0.6359 (3)	−0.2717 (2)	0.87759 (13)	0.0562 (5)
O2	0.9087 (3)	−0.0324 (2)	0.90043 (13)	0.0552 (5)
N1	1.3546 (3)	0.6178 (2)	0.34565 (15)	0.0415 (5)
N2	1.4619 (3)	0.7640 (3)	0.39798 (16)	0.0554 (6)
N3	1.5589 (4)	0.7588 (3)	0.25117 (18)	0.0631 (7)
N4	0.9525 (3)	0.2587 (2)	0.41150 (14)	0.0405 (5)
N5	1.0020 (3)	0.2142 (3)	0.57465 (14)	0.0449 (5)
C1	1.0451 (3)	0.3735 (3)	0.35029 (17)	0.0371 (6)
C2	0.9531 (3)	0.3571 (3)	0.25549 (18)	0.0400 (6)
C3	0.8440 (4)	0.2022 (3)	0.20817 (19)	0.0467 (7)
H3	0.8310	0.1086	0.2367	0.056*
C4	0.7545 (4)	0.1842 (4)	0.1200 (2)	0.0577 (8)
H4	0.6815	0.0794	0.0893	0.069*
C5	0.7739 (4)	0.3220 (5)	0.0777 (2)	0.0638 (9)
C6	0.8768 (5)	0.4763 (5)	0.1230 (2)	0.0747 (10)
H6	0.8870	0.5689	0.0941	0.090*
C7	0.9662 (4)	0.4948 (4)	0.2119 (2)	0.0608 (8)
H7	1.0356	0.6001	0.2428	0.073*
C8	1.2142 (3)	0.4906 (3)	0.38863 (17)	0.0397 (6)
C9	1.4181 (4)	0.6178 (3)	0.2594 (2)	0.0566 (8)
H9	1.3688	0.5296	0.2119	0.068*
C10	1.5792 (4)	0.8412 (4)	0.3368 (2)	0.0654 (9)
H10	1.6716	0.9478	0.3522	0.078*
C11	1.0482 (3)	0.2945 (3)	0.49322 (17)	0.0391 (6)
C12	0.8471 (4)	0.0866 (3)	0.57139 (18)	0.0446 (6)
H12	0.7695	0.0518	0.5153	0.054*
C13	0.7873 (4)	−0.0064 (3)	0.65205 (17)	0.0410 (6)
C14	0.8979 (4)	0.0432 (3)	0.73899 (18)	0.0415 (6)
H14	1.0110	0.1368	0.7476	0.050*
C15	0.8307 (4)	−0.0528 (3)	0.80944 (17)	0.0408 (6)
C16	0.6653 (4)	−0.1945 (3)	0.79674 (17)	0.0417 (6)
C17	0.5543 (4)	−0.2444 (3)	0.71386 (19)	0.0486 (7)
H17	0.4418	−0.3387	0.7064	0.058*
C18	0.6187 (4)	−0.1462 (3)	0.64105 (18)	0.0476 (7)
H18	0.5469	−0.1751	0.5833	0.057*
C19	0.7965 (4)	−0.1776 (4)	0.9421 (2)	0.0573 (8)
H19A	0.8682	−0.2419	0.9535	0.069*
H19B	0.7577	−0.1477	1.0021	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0435 (4)	0.0462 (4)	0.0375 (4)	0.0076 (3)	−0.0024 (3)	0.0073 (3)
Cl1	0.0629 (6)	0.1850 (12)	0.0413 (5)	0.0219 (6)	−0.0027 (4)	0.0368 (6)
O1	0.0551 (12)	0.0602 (12)	0.0384 (11)	0.0068 (10)	0.0026 (9)	0.0171 (9)
O2	0.0583 (12)	0.0564 (12)	0.0352 (10)	0.0083 (10)	−0.0086 (8)	0.0095 (9)
N1	0.0417 (12)	0.0356 (11)	0.0378 (12)	0.0064 (9)	−0.0009 (9)	0.0067 (9)
N2	0.0574 (15)	0.0413 (13)	0.0444 (13)	−0.0023 (11)	0.0003 (11)	0.0037 (10)
N3	0.0642 (16)	0.0578 (15)	0.0472 (15)	0.0029 (13)	0.0081 (12)	0.0154 (12)
N4	0.0393 (11)	0.0403 (12)	0.0372 (12)	0.0111 (9)	0.0016 (9)	0.0088 (9)
N5	0.0473 (13)	0.0468 (13)	0.0371 (12)	0.0146 (11)	0.0035 (10)	0.0121 (10)
C1	0.0374 (13)	0.0357 (13)	0.0372 (14)	0.0132 (11)	0.0034 (10)	0.0094 (11)
C2	0.0342 (13)	0.0434 (14)	0.0388 (14)	0.0112 (11)	0.0030 (11)	0.0104 (11)
C3	0.0418 (15)	0.0513 (16)	0.0430 (16)	0.0147 (12)	0.0038 (12)	0.0072 (13)
C4	0.0438 (16)	0.072 (2)	0.0447 (17)	0.0142 (15)	−0.0007 (13)	−0.0037 (15)
C5	0.0389 (16)	0.104 (3)	0.0369 (16)	0.0162 (17)	0.0034 (12)	0.0208 (17)
C6	0.061 (2)	0.084 (2)	0.068 (2)	0.0135 (18)	−0.0051 (17)	0.0441 (19)
C7	0.0595 (18)	0.0504 (17)	0.0604 (19)	0.0091 (14)	−0.0096 (15)	0.0207 (15)
C8	0.0425 (14)	0.0368 (13)	0.0361 (14)	0.0122 (11)	0.0027 (11)	0.0066 (11)
C9	0.0624 (19)	0.0473 (16)	0.0419 (16)	0.0044 (14)	0.0076 (13)	0.0044 (13)
C10	0.0628 (19)	0.0509 (17)	0.0515 (19)	−0.0079 (15)	0.0005 (15)	0.0100 (15)
C11	0.0415 (14)	0.0383 (13)	0.0357 (14)	0.0139 (11)	0.0040 (11)	0.0083 (11)
C12	0.0497 (16)	0.0466 (15)	0.0336 (14)	0.0159 (13)	−0.0006 (11)	0.0073 (11)
C13	0.0446 (14)	0.0406 (14)	0.0362 (14)	0.0154 (12)	0.0030 (11)	0.0078 (11)
C14	0.0404 (14)	0.0360 (13)	0.0413 (15)	0.0091 (11)	−0.0014 (11)	0.0058 (11)
C15	0.0439 (14)	0.0425 (14)	0.0331 (14)	0.0159 (12)	−0.0019 (11)	0.0017 (11)
C16	0.0437 (14)	0.0446 (14)	0.0340 (14)	0.0146 (12)	0.0059 (11)	0.0078 (11)
C17	0.0404 (14)	0.0465 (15)	0.0442 (16)	0.0031 (12)	0.0006 (12)	0.0085 (12)
C18	0.0471 (15)	0.0524 (16)	0.0337 (14)	0.0112 (13)	−0.0036 (11)	0.0065 (12)
C19	0.0542 (17)	0.0647 (19)	0.0412 (16)	0.0108 (15)	0.0023 (13)	0.0169 (14)

Geometric parameters (Å, º) top

S1—C8	1.713 (3)	C3—H3	0.9300
S1—C11	1.722 (3)	C4—C5	1.371 (5)
Cl1—C5	1.738 (3)	C4—H4	0.9300
O1—C16	1.370 (3)	C5—C6	1.364 (5)
O1—C19	1.427 (3)	C6—C7	1.383 (4)
O2—C15	1.373 (3)	C6—H6	0.9300
O2—C19	1.429 (3)	C7—H7	0.9300
N1—C9	1.342 (3)	C9—H9	0.9300
N1—N2	1.360 (3)	C10—H10	0.9300
N1—C8	1.421 (3)	C12—C13	1.453 (4)
N2—C10	1.312 (4)	C12—H12	0.9300
N3—C9	1.309 (3)	C13—C18	1.387 (4)
N3—C10	1.336 (4)	C13—C14	1.407 (3)
N4—C11	1.298 (3)	C14—C15	1.354 (4)
N4—C1	1.389 (3)	C14—H14	0.9300
N5—C12	1.275 (3)	C15—C16	1.382 (4)
N5—C11	1.396 (3)	C16—C17	1.361 (4)
C1—C8	1.362 (3)	C17—C18	1.389 (4)
C1—C2	1.469 (3)	C17—H17	0.9300
C2—C3	1.387 (4)	C18—H18	0.9300
C2—C7	1.393 (4)	C19—H19A	0.9700
C3—C4	1.375 (4)	C19—H19B	0.9700

C8—S1—C11	88.10 (12)	N3—C9—H9	124.6
C16—O1—C19	106.1 (2)	N1—C9—H9	124.6
C15—O2—C19	106.3 (2)	N2—C10—N3	116.6 (3)
C9—N1—N2	109.1 (2)	N2—C10—H10	121.7
C9—N1—C8	131.0 (2)	N3—C10—H10	121.7
N2—N1—C8	119.6 (2)	N4—C11—N5	128.8 (2)
C10—N2—N1	101.3 (2)	N4—C11—S1	115.96 (19)
C9—N3—C10	102.1 (2)	N5—C11—S1	115.28 (18)
C11—N4—C1	110.7 (2)	N5—C12—C13	122.4 (2)
C12—N5—C11	118.3 (2)	N5—C12—H12	118.8
C8—C1—N4	113.4 (2)	C13—C12—H12	118.8
C8—C1—C2	128.3 (2)	C18—C13—C14	120.7 (2)
N4—C1—C2	118.3 (2)	C18—C13—C12	118.3 (2)
C3—C2—C7	117.9 (3)	C14—C13—C12	120.9 (2)
C3—C2—C1	120.5 (2)	C15—C14—C13	116.4 (2)
C7—C2—C1	121.6 (2)	C15—C14—H14	121.8
C4—C3—C2	121.4 (3)	C13—C14—H14	121.8
C4—C3—H3	119.3	C14—C15—O2	128.4 (2)
C2—C3—H3	119.3	C14—C15—C16	122.3 (2)
C5—C4—C3	119.5 (3)	O2—C15—C16	109.3 (2)
C5—C4—H4	120.3	C17—C16—O1	127.4 (2)
C3—C4—H4	120.3	C17—C16—C15	122.6 (2)
C6—C5—C4	120.8 (3)	O1—C16—C15	110.1 (2)
C6—C5—Cl1	120.2 (3)	C16—C17—C18	116.1 (2)
C4—C5—Cl1	119.0 (3)	C16—C17—H17	122.0
C5—C6—C7	119.9 (3)	C18—C17—H17	122.0
C5—C6—H6	120.1	C13—C18—C17	121.9 (2)
C7—C6—H6	120.1	C13—C18—H18	119.1
C6—C7—C2	120.6 (3)	C17—C18—H18	119.1
C6—C7—H7	119.7	O1—C19—O2	107.6 (2)
C2—C7—H7	119.7	O1—C19—H19A	110.2
C1—C8—N1	129.6 (2)	O2—C19—H19A	110.2
C1—C8—S1	111.83 (19)	O1—C19—H19B	110.2
N1—C8—S1	118.47 (18)	O2—C19—H19B	110.2
N3—C9—N1	110.8 (2)	H19A—C19—H19B	108.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.93	2.52	3.371 (4)	152

Symmetry code: (i) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₂ClN₅O₂S
M_r	409.85
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	7.8260 (19), 8.929 (2), 14.221 (3)
α, β, γ (°)	94.871 (4), 92.332 (4), 114.170 (4)
V (Å³)	900.2 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.26 × 0.20 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.910, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	4582, 3160, 2302
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.127, 1.01
No. of reflections	3160
No. of parameters	253
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.41

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999) and PLATON (Spek, 2003), SHELXTL.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.93	2.52	3.371 (4)	152.2

Symmetry code: (i) −x+2, −y, −z+1.

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