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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2402–o2403.
Published online 2008 November 20. doi:  10.1107/S1600536808037914
PMCID: PMC2960093

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

Abstract

In the title compound, C10H11ClN4O2S, the triazole ring carries methyl and ethoxy­carbonyl groups and is bound via a methyl­ene bridge to a chloro­thia­zole unit. There is also evidence for significant electron delocalization in the triazolyl system. Intra- and inter­molecular C—H(...)O hydrogen bonds together with strong π–π stacking inter­actions [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 [triangle]), Najim et al. (2004 [triangle]), Abu-Orabi et al. (1989 [triangle]), Shuto et al. (1995 [triangle]), Fan & Katritsky (1996 [triangle]), Chen et al. (2005 [triangle]) and Liu et al. (2001 [triangle]). For the synthesis, see: Chen et al. (2007 [triangle]); Chen & Shi (2008 [triangle]). For bond-length data, see: Sasada (1984 [triangle]); Wang et al. (1998 [triangle]). For related literature, see: Chen et al. (2007 [triangle]); Tian et al. (2008 [triangle]); Chen et al. (2008 [triangle]); Knox & Rogers (1989 [triangle]); Rogers et al. (1985 [triangle]); Shuto et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2402-scheme1.jpg

Experimental

Crystal data

  • C10H11ClN4O2S
  • M r = 286.74
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2402-efi1.jpg
  • 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 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

The authors gratefully acknowledge financial support of this work by Yunyang Medical College, and acknowledge the Sophisticated Analytical Instrument Facility, Central China Normal University, Whuhan, for the data collection.

supplementary crystallographic information

Comment

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 (Ogura et al., 2000; Najim et al., 2004; Abu-Orabi et al., 1989; Shuto et al.,1995; Fan & Katritsky, 1996; Chen et al., 2005; Richard & Ben, 1985; Ingrid et al., 1989 and Liu et al., 2001). Since 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, (I) (Fig. 1), which was synthesized by introducing pyridine rings into a 1,2,3-triazole molecular framework.

In the title compound, the C5—N2 and C6—N4 bonds are significantly shorter than that of the single bond of C—N (1.47 Å; Sasada, 1984) and close to the value of the double bond of C—N (1.28 Å; Wang et al., 1998). This indicates significant electron delocalization in the triazolyl system.

Inter and intramolecular C—H···O hydrogen bonds contribute strongly to the stability of the molecular configuration (Fig.2). Strong π—π stacking interactions are also found between adjacent S1—C1/N1/C2—C3 rings with centroid-centroid distances 3.620 (1) Å, dihedral angles of 0.03 (1)°, and a shortest interplanar distance of 3.573 Å.

Experimental

Ethyl acetylacetate (2 mmol) and 5-azidomethyl-2-chlorothiazole (2 mmol) were added to a suspension of milled potassium carbonate (2 mmol) in DMSO (10 ml). The mixture was stirred at room temperature for 6 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 0.52 g of the title compound (yield 91%). Colourless crystals of (I) suitable for X-ray structure analysis were grown from acetone and petroleum ether (1:1, v/v).

Refinement

H atoms bonded to C were placed at calculated positions, with C—H distances in the range 0.93 - 0.98Å. They were refined using a riding model, with Uiso(H) = 1.2Ueq(C), or 1.5Ueq(methyl C).

Figures

Fig. 1.
View of the molecular structure of (I), showing the atom labelling scheme and with displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
A partial view of the crystal packing of (I), showing the formation of C—H···O hydrogen-bonding interactions (dashed lines).

Crystal data

C10H11ClN4O2SZ = 2
Mr = 286.74F000 = 296
Triclinic, P1Dx = 1.476 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.9692 (14) ÅCell parameters from 2592 reflections
b = 9.1656 (16) Åθ = 2.4–27.4º
c = 10.4430 (18) ŵ = 0.46 mm1
α = 65.892 (2)ºT = 291 (2) K
β = 67.938 (2)ºBlock, colourless
γ = 80.641 (2)º0.50 × 0.40 × 0.30 mm
V = 645.23 (19) Å3

Data collection

Bruker SMART APEX CCD area-detector diffractometer2005 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.018
Monochromator: graphiteθmax = 25.5º
T = 291(2) Kθmin = 2.4º
[var phi] and ω scansh = −9→9
Absorption correction: nonek = −11→11
4630 measured reflectionsl = −12→12
2332 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-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 reflectionsΔρmax = 0.30 e Å3
165 parametersΔρmin = −0.25 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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.

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

xyzUiso*/Ueq
Cl1−0.01266 (10)0.69136 (8)0.20124 (9)0.0704 (2)
S10.23526 (8)0.46808 (7)0.07021 (7)0.0534 (2)
O10.7825 (3)−0.0891 (2)0.3892 (2)0.0715 (5)
O20.5259 (3)−0.2272 (2)0.5002 (2)0.0718 (6)
N1−0.0923 (3)0.4021 (3)0.2475 (3)0.0674 (6)
N20.4074 (3)0.0929 (2)0.1275 (2)0.0486 (5)
N30.5752 (3)0.1573 (3)0.0531 (2)0.0603 (5)
N40.6709 (3)0.0880 (2)0.1400 (2)0.0567 (5)
C10.0281 (3)0.5109 (3)0.1813 (3)0.0496 (5)
C2−0.0196 (4)0.2725 (3)0.2086 (3)0.0676 (7)
H2−0.08730.18160.24460.081*
C30.1528 (3)0.2836 (3)0.1165 (3)0.0479 (5)
C40.2660 (4)0.1603 (3)0.0601 (3)0.0584 (6)
H4A0.18870.07500.08300.070*
H4B0.32220.2087−0.04760.070*
C50.3935 (3)−0.0189 (2)0.2639 (2)0.0419 (5)
C60.5634 (3)−0.0210 (2)0.2704 (2)0.0435 (5)
C70.2239 (3)−0.1066 (3)0.3707 (3)0.0611 (7)
H7A0.1451−0.04110.42140.092*
H7B0.2521−0.20380.44240.092*
H7C0.1648−0.13140.31720.092*
C80.6388 (3)−0.1135 (3)0.3903 (3)0.0472 (5)
C90.5797 (5)−0.3295 (3)0.6289 (4)0.0808 (9)
H9A0.6961−0.29580.61630.097*
H9B0.4914−0.31950.71910.097*
C100.5916 (6)−0.4920 (4)0.6429 (4)0.1001 (13)
H10A0.4813−0.52090.64270.150*
H10B0.6104−0.55990.73490.150*
H10C0.6913−0.50450.56050.150*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0673 (4)0.0627 (4)0.0875 (5)0.0081 (3)−0.0224 (4)−0.0417 (4)
S10.0525 (4)0.0453 (3)0.0548 (4)−0.0034 (3)−0.0102 (3)−0.0180 (3)
O10.0572 (11)0.0679 (12)0.0968 (14)−0.0051 (9)−0.0423 (10)−0.0223 (10)
O20.0735 (12)0.0639 (11)0.0695 (11)−0.0188 (9)−0.0428 (10)0.0060 (9)
N10.0479 (12)0.0600 (13)0.0824 (15)−0.0036 (10)−0.0144 (11)−0.0218 (12)
N20.0597 (12)0.0394 (9)0.0494 (10)0.0052 (9)−0.0230 (9)−0.0176 (8)
N30.0638 (13)0.0530 (12)0.0515 (11)−0.0068 (10)−0.0123 (10)−0.0125 (9)
N40.0518 (11)0.0514 (11)0.0573 (12)−0.0067 (9)−0.0114 (9)−0.0157 (10)
C10.0496 (12)0.0485 (12)0.0504 (12)0.0045 (10)−0.0207 (10)−0.0174 (10)
C20.0589 (16)0.0488 (14)0.092 (2)−0.0081 (12)−0.0286 (14)−0.0188 (14)
C30.0576 (14)0.0418 (11)0.0486 (12)0.0006 (10)−0.0291 (11)−0.0117 (10)
C40.0796 (17)0.0483 (13)0.0613 (15)0.0104 (12)−0.0412 (13)−0.0229 (12)
C50.0455 (11)0.0347 (10)0.0480 (11)0.0035 (9)−0.0177 (9)−0.0182 (9)
C60.0433 (11)0.0354 (10)0.0499 (12)−0.0012 (9)−0.0128 (9)−0.0171 (9)
C70.0465 (13)0.0571 (15)0.0709 (16)−0.0079 (11)−0.0228 (12)−0.0108 (12)
C80.0464 (12)0.0397 (11)0.0621 (14)0.0046 (10)−0.0221 (10)−0.0243 (10)
C90.109 (2)0.0618 (17)0.0772 (19)−0.0068 (17)−0.0621 (19)−0.0026 (15)
C100.162 (4)0.068 (2)0.098 (2)0.034 (2)−0.087 (3)−0.0328 (18)

Geometric parameters (Å, °)

Cl1—C11.715 (2)C3—C41.501 (3)
S1—C11.717 (2)C4—H4A0.9700
S1—C31.726 (2)C4—H4B0.9700
O1—C81.197 (3)C5—C61.378 (3)
O2—C81.328 (3)C5—C71.485 (3)
O2—C91.464 (3)C6—C81.476 (3)
N1—C11.281 (3)C7—H7A0.9600
N1—C21.380 (4)C7—H7B0.9600
N2—C51.349 (3)C7—H7C0.9600
N2—N31.357 (3)C9—C101.427 (5)
N2—C41.470 (3)C9—H9A0.9700
N3—N41.304 (3)C9—H9B0.9700
N4—C61.370 (3)C10—H10A0.9600
C2—C31.340 (4)C10—H10B0.9600
C2—H20.9300C10—H10C0.9600
C1—S1—C388.37 (12)C6—C5—C7133.6 (2)
C8—O2—C9118.2 (2)N4—C6—C5109.60 (19)
C1—N1—C2108.7 (2)N4—C6—C8119.0 (2)
C5—N2—N3111.70 (19)C5—C6—C8131.4 (2)
C5—N2—C4129.3 (2)C5—C7—H7A109.5
N3—N2—C4118.8 (2)C5—C7—H7B109.5
N4—N3—N2107.38 (18)H7A—C7—H7B109.5
N3—N4—C6108.2 (2)C5—C7—H7C109.5
N1—C1—Cl1122.4 (2)H7A—C7—H7C109.5
N1—C1—S1116.79 (19)H7B—C7—H7C109.5
Cl1—C1—S1120.83 (14)O1—C8—O2124.3 (2)
C3—C2—N1117.0 (2)O1—C8—C6124.5 (2)
C3—C2—H2121.5O2—C8—C6111.18 (18)
N1—C2—H2121.5C10—C9—O2110.0 (3)
C2—C3—C4128.2 (2)C10—C9—H9A109.7
C2—C3—S1109.13 (19)O2—C9—H9A109.7
C4—C3—S1122.70 (19)C10—C9—H9B109.7
N2—C4—C3111.66 (18)O2—C9—H9B109.7
N2—C4—H4A109.3H9A—C9—H9B108.2
C3—C4—H4A109.3C9—C10—H10A109.5
N2—C4—H4B109.3C9—C10—H10B109.5
C3—C4—H4B109.3H10A—C10—H10B109.5
H4A—C4—H4B107.9C9—C10—H10C109.5
N2—C5—C6103.16 (19)H10A—C10—H10C109.5
N2—C5—C7123.2 (2)H10B—C10—H10C109.5
C5—N2—N3—N40.1 (3)C4—N2—C5—C6−173.8 (2)
C4—N2—N3—N4174.52 (19)N3—N2—C5—C7178.8 (2)
N2—N3—N4—C6−0.1 (3)C4—N2—C5—C75.1 (3)
C2—N1—C1—Cl1179.52 (19)N3—N4—C6—C50.0 (3)
C2—N1—C1—S1−0.5 (3)N3—N4—C6—C8−178.4 (2)
C3—S1—C1—N10.1 (2)N2—C5—C6—N40.0 (2)
C3—S1—C1—Cl1−179.93 (15)C7—C5—C6—N4−178.6 (2)
C1—N1—C2—C30.8 (4)N2—C5—C6—C8178.2 (2)
N1—C2—C3—C4178.2 (2)C7—C5—C6—C8−0.4 (4)
N1—C2—C3—S1−0.8 (3)C9—O2—C8—O10.2 (4)
C1—S1—C3—C20.38 (19)C9—O2—C8—C6−179.5 (2)
C1—S1—C3—C4−178.66 (19)N4—C6—C8—O18.3 (3)
C5—N2—C4—C378.7 (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—O210.0 (3)
S1—C3—C4—N269.9 (3)C8—O2—C9—C10−119.0 (3)
N3—N2—C5—C6−0.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···O1i0.932.473.375 (4)164
C7—H7B···O20.962.433.033 (4)121
C9—H9A···O10.972.282.710 (4)106

Symmetry codes: (i) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2677).

References

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