Ethyl 1-[(2-chloro-1,3-thia-zol-5-yl)methyl]-5-methyl-1H-1,2,3-triazole-4-carboxylate.

In the title compound, C(10)H(11)ClN(4)O(2)S, the triazole ring carries methyl and ethoxy-carbonyl groups and is bound via a methyl-ene bridge to a chloro-thia-zole unit. There is also evidence for significant electron delocalization in the triazolyl system. Intra- and inter-molecular C-H⋯O hydrogen bonds together with strong π-π stacking inter-actions [centroid-centroid distance 3.620 (1) Å] stabilize the structure.

Related literature

Many derivatives of triazole have been prepared, and their biological activities have been studied by Ogura et al. (2000 ▶), Najim et al. (2004 ▶), Abu-Orabi et al. (1989 ▶), Shuto et al. (1995 ▶), Fan & Katritsky (1996 ▶), Chen et al. (2005 ▶) and Liu et al. (2001 ▶). For the synthesis, see: Chen et al. (2007 ▶); Chen & Shi (2008 ▶). For bond-length data, see: Sasada (1984 ▶); Wang et al. (1998 ▶). For related literature, see: Chen et al. (2007 ▶); Tian et al. (2008 ▶); Chen et al. (2008 ▶); Knox & Rogers (1989 ▶); Rogers et al. (1985 ▶); Shuto et al. (1995 ▶).

Experimental

Crystal data

C10H11ClN4O2S

M = 286.74

Triclinic,

a = 7.9692 (14) Å

b = 9.1656 (16) Å

c = 10.4430 (18) Å

α = 65.892 (2)°

β = 67.938 (2)°

γ = 80.641 (2)°

V = 645.23 (19) Å3

Z = 2

Mo Kα radiation

μ = 0.46 mm−1

T = 291 (2) K

0.50 × 0.40 × 0.30 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: none

4630 measured reflections

2332 independent reflections

2005 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.118

S = 1.04

2332 reflections

165 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.25 e Å−3

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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037914/at2677sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037914/at2677Isup2.hkl

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

C10H11ClN4O2S	Z = 2
Mr = 286.74	F000 = 296
Triclinic, P1	Dx = 1.476 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 7.9692 (14) Å	Cell parameters from 2592 reflections
b = 9.1656 (16) Å	θ = 2.4–27.4º
c = 10.4430 (18) Å	µ = 0.46 mm−1
α = 65.892 (2)º	T = 291 (2) K
β = 67.938 (2)º	Block, colourless
γ = 80.641 (2)º	0.50 × 0.40 × 0.30 mm
V = 645.23 (19) Å3

Bruker SMART APEX CCD area-detector diffractometer	2005 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Monochromator: graphite	θmax = 25.5º
T = 291(2) K	θmin = 2.4º
φ and ω scans	h = −9→9
Absorption correction: none	k = −11→11
4630 measured reflections	l = −12→12
2332 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041	H-atom parameters constrained
wR(F2) = 0.118	w = 1/[σ2(Fo2) + (0.062P)2 + 0.2829P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2332 reflections	Δρmax = 0.30 e Å−3
165 parameters	Δρmin = −0.25 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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 andgoodness of fit S are based on F2, conventional R-factors R are basedon F, with F set to zero for negative F2. The threshold expression ofF2 > σ(F2) is used only for calculating R-factors(gt) etc. and isnot relevant to the choice of reflections for refinement. R-factors basedon F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Cl1	−0.01266 (10)	0.69136 (8)	0.20124 (9)	0.0704 (2)
S1	0.23526 (8)	0.46808 (7)	0.07021 (7)	0.0534 (2)
O1	0.7825 (3)	−0.0891 (2)	0.3892 (2)	0.0715 (5)
O2	0.5259 (3)	−0.2272 (2)	0.5002 (2)	0.0718 (6)
N1	−0.0923 (3)	0.4021 (3)	0.2475 (3)	0.0674 (6)
N2	0.4074 (3)	0.0929 (2)	0.1275 (2)	0.0486 (5)
N3	0.5752 (3)	0.1573 (3)	0.0531 (2)	0.0603 (5)
N4	0.6709 (3)	0.0880 (2)	0.1400 (2)	0.0567 (5)
C1	0.0281 (3)	0.5109 (3)	0.1813 (3)	0.0496 (5)
C2	−0.0196 (4)	0.2725 (3)	0.2086 (3)	0.0676 (7)
H2	−0.0873	0.1816	0.2446	0.081*
C3	0.1528 (3)	0.2836 (3)	0.1165 (3)	0.0479 (5)
C4	0.2660 (4)	0.1603 (3)	0.0601 (3)	0.0584 (6)
H4A	0.1887	0.0750	0.0830	0.070*
H4B	0.3222	0.2087	−0.0476	0.070*
C5	0.3935 (3)	−0.0189 (2)	0.2639 (2)	0.0419 (5)
C6	0.5634 (3)	−0.0210 (2)	0.2704 (2)	0.0435 (5)
C7	0.2239 (3)	−0.1066 (3)	0.3707 (3)	0.0611 (7)
H7A	0.1451	−0.0411	0.4214	0.092*
H7B	0.2521	−0.2038	0.4424	0.092*
H7C	0.1648	−0.1314	0.3172	0.092*
C8	0.6388 (3)	−0.1135 (3)	0.3903 (3)	0.0472 (5)
C9	0.5797 (5)	−0.3295 (3)	0.6289 (4)	0.0808 (9)
H9A	0.6961	−0.2958	0.6163	0.097*
H9B	0.4914	−0.3195	0.7191	0.097*
C10	0.5916 (6)	−0.4920 (4)	0.6429 (4)	0.1001 (13)
H10A	0.4813	−0.5209	0.6427	0.150*
H10B	0.6104	−0.5599	0.7349	0.150*
H10C	0.6913	−0.5045	0.5605	0.150*

	U11	U22	U33	U12	U13	U23
Cl1	0.0673 (4)	0.0627 (4)	0.0875 (5)	0.0081 (3)	−0.0224 (4)	−0.0417 (4)
S1	0.0525 (4)	0.0453 (3)	0.0548 (4)	−0.0034 (3)	−0.0102 (3)	−0.0180 (3)
O1	0.0572 (11)	0.0679 (12)	0.0968 (14)	−0.0051 (9)	−0.0423 (10)	−0.0223 (10)
O2	0.0735 (12)	0.0639 (11)	0.0695 (11)	−0.0188 (9)	−0.0428 (10)	0.0060 (9)
N1	0.0479 (12)	0.0600 (13)	0.0824 (15)	−0.0036 (10)	−0.0144 (11)	−0.0218 (12)
N2	0.0597 (12)	0.0394 (9)	0.0494 (10)	0.0052 (9)	−0.0230 (9)	−0.0176 (8)
N3	0.0638 (13)	0.0530 (12)	0.0515 (11)	−0.0068 (10)	−0.0123 (10)	−0.0125 (9)
N4	0.0518 (11)	0.0514 (11)	0.0573 (12)	−0.0067 (9)	−0.0114 (9)	−0.0157 (10)
C1	0.0496 (12)	0.0485 (12)	0.0504 (12)	0.0045 (10)	−0.0207 (10)	−0.0174 (10)
C2	0.0589 (16)	0.0488 (14)	0.092 (2)	−0.0081 (12)	−0.0286 (14)	−0.0188 (14)
C3	0.0576 (14)	0.0418 (11)	0.0486 (12)	0.0006 (10)	−0.0291 (11)	−0.0117 (10)
C4	0.0796 (17)	0.0483 (13)	0.0613 (15)	0.0104 (12)	−0.0412 (13)	−0.0229 (12)
C5	0.0455 (11)	0.0347 (10)	0.0480 (11)	0.0035 (9)	−0.0177 (9)	−0.0182 (9)
C6	0.0433 (11)	0.0354 (10)	0.0499 (12)	−0.0012 (9)	−0.0128 (9)	−0.0171 (9)
C7	0.0465 (13)	0.0571 (15)	0.0709 (16)	−0.0079 (11)	−0.0228 (12)	−0.0108 (12)
C8	0.0464 (12)	0.0397 (11)	0.0621 (14)	0.0046 (10)	−0.0221 (10)	−0.0243 (10)
C9	0.109 (2)	0.0618 (17)	0.0772 (19)	−0.0068 (17)	−0.0621 (19)	−0.0026 (15)
C10	0.162 (4)	0.068 (2)	0.098 (2)	0.034 (2)	−0.087 (3)	−0.0328 (18)

Cl1—C1	1.715 (2)	C3—C4	1.501 (3)
S1—C1	1.717 (2)	C4—H4A	0.9700
S1—C3	1.726 (2)	C4—H4B	0.9700
O1—C8	1.197 (3)	C5—C6	1.378 (3)
O2—C8	1.328 (3)	C5—C7	1.485 (3)
O2—C9	1.464 (3)	C6—C8	1.476 (3)
N1—C1	1.281 (3)	C7—H7A	0.9600
N1—C2	1.380 (4)	C7—H7B	0.9600
N2—C5	1.349 (3)	C7—H7C	0.9600
N2—N3	1.357 (3)	C9—C10	1.427 (5)
N2—C4	1.470 (3)	C9—H9A	0.9700
N3—N4	1.304 (3)	C9—H9B	0.9700
N4—C6	1.370 (3)	C10—H10A	0.9600
C2—C3	1.340 (4)	C10—H10B	0.9600
C2—H2	0.9300	C10—H10C	0.9600
C1—S1—C3	88.37 (12)	C6—C5—C7	133.6 (2)
C8—O2—C9	118.2 (2)	N4—C6—C5	109.60 (19)
C1—N1—C2	108.7 (2)	N4—C6—C8	119.0 (2)
C5—N2—N3	111.70 (19)	C5—C6—C8	131.4 (2)
C5—N2—C4	129.3 (2)	C5—C7—H7A	109.5
N3—N2—C4	118.8 (2)	C5—C7—H7B	109.5
N4—N3—N2	107.38 (18)	H7A—C7—H7B	109.5
N3—N4—C6	108.2 (2)	C5—C7—H7C	109.5
N1—C1—Cl1	122.4 (2)	H7A—C7—H7C	109.5
N1—C1—S1	116.79 (19)	H7B—C7—H7C	109.5
Cl1—C1—S1	120.83 (14)	O1—C8—O2	124.3 (2)
C3—C2—N1	117.0 (2)	O1—C8—C6	124.5 (2)
C3—C2—H2	121.5	O2—C8—C6	111.18 (18)
N1—C2—H2	121.5	C10—C9—O2	110.0 (3)
C2—C3—C4	128.2 (2)	C10—C9—H9A	109.7
C2—C3—S1	109.13 (19)	O2—C9—H9A	109.7
C4—C3—S1	122.70 (19)	C10—C9—H9B	109.7
N2—C4—C3	111.66 (18)	O2—C9—H9B	109.7
N2—C4—H4A	109.3	H9A—C9—H9B	108.2
C3—C4—H4A	109.3	C9—C10—H10A	109.5
N2—C4—H4B	109.3	C9—C10—H10B	109.5
C3—C4—H4B	109.3	H10A—C10—H10B	109.5
H4A—C4—H4B	107.9	C9—C10—H10C	109.5
N2—C5—C6	103.16 (19)	H10A—C10—H10C	109.5
N2—C5—C7	123.2 (2)	H10B—C10—H10C	109.5
C5—N2—N3—N4	0.1 (3)	C4—N2—C5—C6	−173.8 (2)
C4—N2—N3—N4	174.52 (19)	N3—N2—C5—C7	178.8 (2)
N2—N3—N4—C6	−0.1 (3)	C4—N2—C5—C7	5.1 (3)
C2—N1—C1—Cl1	179.52 (19)	N3—N4—C6—C5	0.0 (3)
C2—N1—C1—S1	−0.5 (3)	N3—N4—C6—C8	−178.4 (2)
C3—S1—C1—N1	0.1 (2)	N2—C5—C6—N4	0.0 (2)
C3—S1—C1—Cl1	−179.93 (15)	C7—C5—C6—N4	−178.6 (2)
C1—N1—C2—C3	0.8 (4)	N2—C5—C6—C8	178.2 (2)
N1—C2—C3—C4	178.2 (2)	C7—C5—C6—C8	−0.4 (4)
N1—C2—C3—S1	−0.8 (3)	C9—O2—C8—O1	0.2 (4)
C1—S1—C3—C2	0.38 (19)	C9—O2—C8—C6	−179.5 (2)
C1—S1—C3—C4	−178.66 (19)	N4—C6—C8—O1	8.3 (3)
C5—N2—C4—C3	78.7 (3)	C5—C6—C8—O1	−169.7 (2)
N3—N2—C4—C3	−94.6 (3)	N4—C6—C8—O2	−171.9 (2)
C2—C3—C4—N2	−109.0 (3)	C5—C6—C8—O2	10.0 (3)
S1—C3—C4—N2	69.9 (3)	C8—O2—C9—C10	−119.0 (3)
N3—N2—C5—C6	−0.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1i	0.93	2.47	3.375 (4)	164
C7—H7B···O2	0.96	2.43	3.033 (4)	121
C9—H9A···O1	0.97	2.28	2.710 (4)	106

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1i	0.93	2.47	3.375 (4)	164
C7—H7B⋯O2	0.96	2.43	3.033 (4)	121

Symmetry code: (i) .