1-{1-[(2-Chloro­thia­zol-5-yl)meth­yl]-5-methyl-1H-1,2,3-triazol-4-yl}ethanone

Chen, X.-B.; Tian, J.-H.; Xu, J.; Yu, Y.; Wang, Q.

doi:10.1107/S1600536809042937

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2840

https://doi.org/10.1107/S1600536809042937

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1-{1-[(2-Chlorothiazol-5-yl)methyl]-5-methyl-1H-1,2,3-triazol-4-yl}ethanone

Xiao-Bao Chen,^a ^* Jia-Hua Tian,^a Jing Xu,^a Yong Yu ^a and Qun Wang ^a

^aInstitute of Medicinal Chemistry, Yunyang Medical College, Shiyan, 442000, People's Republic of China
^*Correspondence e-mail: chenxiaobao@yahoo.com.cn

(Received 18 October 2009; accepted 19 October 2009; online 23 October 2009)

In the title compound, C₉H₉ClN₄OS, the two rings enclose a dihedral angle of 84.67 (11)°. Intermolecular C—H⋯O and C—H⋯N hydrogen bonds stabilize the crystal packing.

Related literature

For the biological activity of triazole derivatives, see Najim et al. (2004 ); Liu et al. (2001 ). For the synthesis of the title compound, see: Chen & Shi (2008 ).

Experimental

Crystal data

C₉H₉ClN₄OS
M_r = 256.71
Orthorhombic, P b c a
a = 10.5421 (6) Å
b = 11.1494 (6) Å
c = 19.8557 (10) Å
V = 2333.8 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 298 K
0.16 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: none
22708 measured reflections
2556 independent reflections
2336 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.128
S = 1.15
2556 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4B⋯N3ⁱ	0.97	2.48	3.399 (3)	159
C4—H4A⋯O1ⁱⁱ	0.97	2.48	3.376 (3)	153
C7—H7C⋯O1ⁱⁱ	0.96	2.57	3.396 (3)	144
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809042937/bt5103sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809042937/bt5103Isup2.hkl

checkCIF report

Comment top

It is well known that many triazole-related molecules play an important role in the development of agrochemicals such as insecticides, nematocides, acaricide and plant growth regulators ( Najim et al., 2004; Liu et al., 2001). The structure-activity relationship is very useful in the rational design of pharmaceuticals and agrochemicals. We report here the crystal structure of the title compound (Fig. 1), which was synthesized by adding a thiazole rings to a 1,2,3-Triazole molecular framework. Intermolecular C—H···O and C—H···N hydrogen bonds contribute strongly to the stability of the crystal packing (Fig. 2).

Related literature top

For the biological activity of triazole derivatives, see Najim et al. (2004); Liu et al. (2001). For the synthesis of the title compound, see: Chen & Shi (2008).

Experimental top

Acetylacetone (2 mmol) and 5-azidomethyl-2-chlorothiazole (2 mmol) were added to a suspension of milled potassium carbonate (6 mmol) in DMSO (10 ml). The mixture was stirred at room temperature for 10 h (monitored by thin-layer chromatography) and poured to water (50 ml). The solid was collected by filtration, washed with water and diethyl ether, respectively, and dried to give 0.46 g of the title compound (yield 90%). Colorless crystals of (I) suitable for X-ray structure analysis were grown from acetone and petroleum ether (1:3, v/v).

Structure description top

For the biological activity of triazole derivatives, see Najim et al. (2004); Liu et al. (2001). For the synthesis of the title compound, see: Chen & Shi (2008).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the molecular structure of the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial view of the crystal packing of the title compound, showing the C—H···O and C—H···N hydrogen bonds as dashed lines.

1-{1-[(2-Chlorothiazol-5-yl)methyl]-5-methyl-1H-1,2,3-triazol-4- yl}ethanone top

Crystal data top

C₉H₉ClN₄OS	D_x = 1.461 Mg m⁻³
M_r = 256.71	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9847 reflections
a = 10.5421 (6) Å	θ = 2.8–28.3°
b = 11.1494 (6) Å	µ = 0.49 mm⁻¹
c = 19.8557 (10) Å	T = 298 K
V = 2333.8 (2) Å³	Block, colorless
Z = 8	0.16 × 0.10 × 0.10 mm
F(000) = 1056

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2336 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.046
Graphite monochromator	θ_max = 27.0°, θ_min = 2.1°
φ and ω scans	h = −13→13
22708 measured reflections	k = −14→14
2556 independent reflections	l = −25→25

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) = 0.128	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0593P)² + 0.9336P] where P = (F_o² + 2F_c²)/3
2556 reflections	(Δ/σ)_max = 0.002
147 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₉H₉ClN₄OS	V = 2333.8 (2) Å³
M_r = 256.71	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.5421 (6) Å	µ = 0.49 mm⁻¹
b = 11.1494 (6) Å	T = 298 K
c = 19.8557 (10) Å	0.16 × 0.10 × 0.10 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2336 reflections with I > 2σ(I)
22708 measured reflections	R_int = 0.046
2556 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.15	Δρ_max = 0.29 e Å⁻³
2556 reflections	Δρ_min = −0.19 e Å⁻³
147 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
C1	0.06077 (19)	0.5833 (2)	0.07494 (12)	0.0523 (5)
C2	0.1710 (2)	0.4540 (2)	0.13106 (13)	0.0611 (6)
H2	0.1838	0.3914	0.1613	0.073*
C3	0.26783 (19)	0.50485 (18)	0.09799 (9)	0.0425 (4)
C4	0.40502 (19)	0.47144 (17)	0.10133 (10)	0.0433 (4)
H4A	0.4171	0.4137	0.1373	0.052*
H4B	0.4291	0.4331	0.0594	0.052*
C5	0.50309 (18)	0.64274 (16)	0.16817 (9)	0.0389 (4)
C6	0.59612 (18)	0.72323 (17)	0.14998 (9)	0.0403 (4)
C7	0.4283 (3)	0.6266 (2)	0.23107 (11)	0.0649 (7)
H7A	0.3395	0.6336	0.2211	0.097*
H7B	0.4519	0.6872	0.2631	0.097*
H7C	0.4452	0.5488	0.2497	0.097*
C8	0.6563 (2)	0.81698 (19)	0.19098 (11)	0.0492 (5)
C9	0.7538 (2)	0.8946 (2)	0.15856 (13)	0.0637 (6)
H9A	0.7830	0.9533	0.1903	0.096*
H9B	0.7173	0.9344	0.1203	0.096*
H9C	0.8239	0.8460	0.1441	0.096*
Cl1	−0.06811 (6)	0.66155 (7)	0.04706 (5)	0.0803 (3)
N1	0.05217 (18)	0.4984 (2)	0.11826 (11)	0.0659 (6)
N2	0.48829 (14)	0.57468 (14)	0.11306 (7)	0.0380 (3)
N3	0.56710 (16)	0.61037 (18)	0.06291 (9)	0.0499 (4)
N4	0.63206 (16)	0.70047 (17)	0.08532 (8)	0.0498 (4)
O1	0.6277 (2)	0.82866 (17)	0.24974 (9)	0.0745 (5)
S1	0.21063 (5)	0.61575 (6)	0.04596 (3)	0.0553 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0380 (10)	0.0567 (12)	0.0623 (13)	−0.0021 (9)	0.0002 (9)	−0.0114 (11)
C2	0.0553 (13)	0.0692 (15)	0.0589 (13)	−0.0073 (11)	0.0030 (10)	0.0170 (11)
C3	0.0443 (10)	0.0455 (10)	0.0376 (9)	−0.0051 (8)	−0.0020 (8)	−0.0005 (8)
C4	0.0475 (10)	0.0421 (10)	0.0405 (9)	−0.0010 (8)	−0.0026 (8)	−0.0021 (8)
C5	0.0438 (10)	0.0384 (9)	0.0344 (9)	0.0058 (8)	−0.0010 (7)	−0.0005 (7)
C6	0.0385 (9)	0.0433 (10)	0.0391 (9)	0.0041 (7)	−0.0016 (7)	−0.0009 (7)
C7	0.0893 (19)	0.0635 (14)	0.0419 (11)	−0.0171 (13)	0.0195 (11)	−0.0072 (10)
C8	0.0520 (11)	0.0442 (10)	0.0514 (12)	0.0021 (9)	−0.0063 (9)	−0.0048 (9)
C9	0.0555 (13)	0.0612 (14)	0.0745 (15)	−0.0125 (11)	−0.0003 (12)	−0.0112 (12)
Cl1	0.0474 (4)	0.0764 (5)	0.1170 (6)	0.0117 (3)	−0.0114 (3)	−0.0108 (4)
N1	0.0470 (11)	0.0823 (15)	0.0683 (13)	−0.0106 (10)	0.0095 (9)	0.0072 (11)
N2	0.0367 (8)	0.0438 (8)	0.0333 (7)	0.0019 (6)	−0.0005 (6)	−0.0020 (6)
N3	0.0494 (10)	0.0628 (11)	0.0375 (8)	−0.0066 (8)	0.0062 (7)	−0.0066 (8)
N4	0.0462 (9)	0.0611 (11)	0.0423 (9)	−0.0072 (8)	0.0063 (7)	−0.0067 (8)
O1	0.1052 (15)	0.0692 (11)	0.0490 (9)	−0.0220 (10)	0.0015 (9)	−0.0161 (8)
S1	0.0431 (3)	0.0575 (4)	0.0653 (4)	−0.0022 (2)	−0.0006 (2)	0.0173 (2)

Geometric parameters (Å, º) top

C1—N1	1.283 (3)	C5—C7	1.488 (3)
C1—Cl1	1.707 (2)	C6—N4	1.362 (2)
C1—S1	1.720 (2)	C6—C8	1.469 (3)
C2—C3	1.340 (3)	C7—H7A	0.9600
C2—N1	1.371 (3)	C7—H7B	0.9600
C2—H2	0.9300	C7—H7C	0.9600
C3—C4	1.495 (3)	C8—O1	1.212 (3)
C3—S1	1.720 (2)	C8—C9	1.490 (3)
C4—N2	1.466 (2)	C9—H9A	0.9600
C4—H4A	0.9700	C9—H9B	0.9600
C4—H4B	0.9700	C9—H9C	0.9600
C5—N2	1.341 (2)	N2—N3	1.357 (2)
C5—C6	1.378 (3)	N3—N4	1.295 (3)

N1—C1—Cl1	122.58 (17)	C5—C7—H7B	109.5
N1—C1—S1	116.39 (17)	H7A—C7—H7B	109.5
Cl1—C1—S1	121.03 (15)	C5—C7—H7C	109.5
C3—C2—N1	116.9 (2)	H7A—C7—H7C	109.5
C3—C2—H2	121.6	H7B—C7—H7C	109.5
N1—C2—H2	121.6	O1—C8—C6	120.2 (2)
C2—C3—C4	127.6 (2)	O1—C8—C9	121.7 (2)
C2—C3—S1	109.37 (17)	C6—C8—C9	118.14 (19)
C4—C3—S1	123.01 (14)	C8—C9—H9A	109.5
N2—C4—C3	113.00 (16)	C8—C9—H9B	109.5
N2—C4—H4A	109.0	H9A—C9—H9B	109.5
C3—C4—H4A	109.0	C8—C9—H9C	109.5
N2—C4—H4B	109.0	H9A—C9—H9C	109.5
C3—C4—H4B	109.0	H9B—C9—H9C	109.5
H4A—C4—H4B	107.8	C1—N1—C2	109.05 (19)
N2—C5—C6	103.75 (16)	C5—N2—N3	111.21 (16)
N2—C5—C7	123.72 (18)	C5—N2—C4	130.06 (16)
C6—C5—C7	132.53 (18)	N3—N2—C4	118.71 (15)
N4—C6—C5	108.88 (17)	N4—N3—N2	107.41 (15)
N4—C6—C8	122.34 (18)	N3—N4—C6	108.75 (16)
C5—C6—C8	128.73 (18)	C1—S1—C3	88.29 (11)
C5—C7—H7A	109.5

N1—C2—C3—C4	−178.2 (2)	C6—C5—N2—N3	−0.2 (2)
N1—C2—C3—S1	−0.6 (3)	C7—C5—N2—N3	178.9 (2)
C2—C3—C4—N2	−130.4 (2)	C6—C5—N2—C4	178.39 (17)
S1—C3—C4—N2	52.3 (2)	C7—C5—N2—C4	−2.5 (3)
N2—C5—C6—N4	0.3 (2)	C3—C4—N2—C5	69.8 (2)
C7—C5—C6—N4	−178.7 (2)	C3—C4—N2—N3	−111.75 (19)
N2—C5—C6—C8	−177.00 (18)	C5—N2—N3—N4	0.0 (2)
C7—C5—C6—C8	4.0 (4)	C4—N2—N3—N4	−178.78 (17)
N4—C6—C8—O1	−174.8 (2)	N2—N3—N4—C6	0.2 (2)
C5—C6—C8—O1	2.2 (3)	C5—C6—N4—N3	−0.4 (2)
N4—C6—C8—C9	4.2 (3)	C8—C6—N4—N3	177.18 (18)
C5—C6—C8—C9	−178.8 (2)	N1—C1—S1—C3	−0.6 (2)
Cl1—C1—N1—C2	−179.37 (19)	Cl1—C1—S1—C3	179.14 (15)
S1—C1—N1—C2	0.4 (3)	C2—C3—S1—C1	0.65 (18)
C3—C2—N1—C1	0.2 (3)	C4—C3—S1—C1	178.39 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···N3ⁱ	0.97	2.48	3.399 (3)	159
C4—H4A···O1ⁱⁱ	0.97	2.48	3.376 (3)	153
C7—H7C···O1ⁱⁱ	0.96	2.57	3.396 (3)	144

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₉ClN₄OS
M_r	256.71
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	10.5421 (6), 11.1494 (6), 19.8557 (10)
V (Å³)	2333.8 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.16 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	22708, 2556, 2336
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.128, 1.15
No. of reflections	2556
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.19

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4B···N3ⁱ	0.97	2.48	3.399 (3)	158.8
C4—H4A···O1ⁱⁱ	0.97	2.48	3.376 (3)	153.4
C7—H7C···O1ⁱⁱ	0.96	2.57	3.396 (3)	144.0

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors gratefully acknowledge financial support of this work by Yunyang Medical College (grant No. 2007ZQB24).

References

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