PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2352.
Published online 2008 November 13. doi:  10.1107/S1600536808037197
PMCID: PMC2959854

Ethyl 1-(6-chloro-3-pyridylmeth­yl)-5-ethoxy­methyl­eneamino-1H-1,2,3-triazole-4-carboxyl­ate

Abstract

In the title compound, C14H16ClN5O3, there is evidence for significant electron delocalization in the triazolyl system. Intra­molecular C—H(...)O and inter­molecular C—H(...)O and C—H(...)N hydrogen bonds stabilize the structure.

Related literature

Many derivatives of triazole have been prepared, and their biological activities have been studied, see: Ogura et al. (2000a [triangle],b [triangle]); Najim et al. (2004 [triangle]); Banks & Chubb (1999a [triangle],b [triangle]); Shuto et al. (1995a [triangle],b [triangle]); Yuan et al. (2006 [triangle]); Chen et al. (2005 [triangle]); Liu et al. (2001 [triangle]). For the synthesis, see: Chen & Shi (2008 [triangle]). For bond-length data, see: Sasada (1984 [triangle]); Wang et al. (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2352-scheme1.jpg

Experimental

Crystal data

  • C14H16ClN5O3
  • M r = 337.77
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2352-efi1.jpg
  • a = 16.8823 (17) Å
  • b = 6.3134 (6) Å
  • c = 15.3065 (15) Å
  • β = 90.980 (1)°
  • V = 1631.2 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.26 mm−1
  • T = 291 (2) K
  • 0.50 × 0.47 × 0.36 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: none
  • 10092 measured reflections
  • 2980 independent reflections
  • 2551 reflections with I > 2σ(I)
  • R int = 0.014

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.098
  • S = 1.04
  • 2980 reflections
  • 210 parameters
  • H-atom parameters constrained
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.40 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/S1600536808037197/at2675sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808037197/at2675Isup2.hkl

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

Acknowledgments

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

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., 2000a,b; Najim et al., 2004; Banks & Chubb, 1999a,b); Shuto et al., 1995a,b; Yuan et al., 2006; Chen et al., 2005 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 (I), the C7—N4 and C11—N2 bonds [1.366 (2) and 1.348 (2) Å] 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. Intramolecular C—H···O and intermolecular C—H···O and C—H···N hydrogen bonds contribute strongly to the stability of the molecular configuration (Fig.2, Table 1).

Experimental

A solution of compound 1-((6-chloropyridin-3-yl)methyl)-4-ethoxycarbonyl-5-amine-1H-1,2,3- triazole (2 mmol) in triethyl ortho formate (10 ml) was refluxed for 4 h, cooled briefly and evaporated. The residue was purified by chromatography on a silica gel column by eluting with petroleum ether/acetone (2:1, v/v) to give the title compound (yield 75%). Colourless crystals of (I) suitable for X-ray structure analysis were grown from acetone and petroleum ether (1:3, v/v).

Refinement

H atoms bonded to C were placed at calculated positions, with C—H = 0.93–0.97 Å and 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 and C—H···N hydrogen-bonding interactions (dashed lines).

Crystal data

C14H16ClN5O3F000 = 704
Mr = 337.77Dx = 1.375 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4752 reflections
a = 16.8823 (17) Åθ = 2.7–27.8º
b = 6.3134 (6) ŵ = 0.26 mm1
c = 15.3065 (15) ÅT = 291 (2) K
β = 90.9800 (10)ºBlock, colourless
V = 1631.2 (3) Å30.50 × 0.47 × 0.36 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer2551 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.014
Monochromator: graphiteθmax = 25.5º
T = 291(2) Kθmin = 2.7º
[var phi] and ω scansh = −20→20
Absorption correction: nonek = −7→7
10092 measured reflectionsl = −18→18
2980 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)] = 0.036H-atom parameters constrained
wR(F2) = 0.098  w = 1/[σ2(Fo2) + (0.0449P)2 + 0.5005P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2980 reflectionsΔρmax = 0.25 e Å3
210 parametersΔρmin = −0.40 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
Cl10.36873 (3)0.34616 (9)0.06142 (3)0.07336 (19)
O10.89923 (7)0.8586 (2)−0.04595 (8)0.0571 (3)
O20.91635 (9)0.6353 (3)0.06636 (11)0.0821 (5)
O30.80412 (9)0.27638 (19)0.22225 (8)0.0633 (4)
N10.50169 (9)0.4258 (2)0.14254 (10)0.0559 (4)
N20.69532 (8)0.9067 (2)0.13235 (8)0.0440 (3)
N30.69871 (8)1.0541 (2)0.06795 (9)0.0499 (3)
N40.76295 (8)1.0162 (2)0.02373 (9)0.0494 (3)
N50.76407 (8)0.6142 (2)0.19200 (8)0.0470 (3)
C10.44375 (10)0.5167 (3)0.09780 (10)0.0480 (4)
C20.43841 (11)0.7289 (3)0.07976 (12)0.0582 (5)
H20.39590.78420.04770.070*
C30.49856 (10)0.8571 (3)0.11104 (12)0.0545 (4)
H30.49721.00210.10040.065*
C40.56076 (9)0.7699 (3)0.15809 (10)0.0422 (4)
C50.55899 (10)0.5546 (3)0.17194 (12)0.0535 (4)
H50.60060.49460.20400.064*
C60.62874 (10)0.9037 (3)0.19223 (11)0.0504 (4)
H6A0.61031.04750.20120.061*
H6B0.64660.84850.24830.061*
C70.80079 (9)0.8443 (2)0.05900 (10)0.0443 (4)
C80.87732 (10)0.7667 (3)0.02805 (12)0.0515 (4)
C90.97474 (11)0.7873 (3)−0.08109 (14)0.0676 (5)
H9A0.97440.6348−0.08850.081*
H9B1.01790.8246−0.04140.081*
C100.98505 (15)0.8939 (5)−0.16692 (17)0.0994 (9)
H10A0.94330.8509−0.20650.149*
H10B1.03530.8547−0.19050.149*
H10C0.98321.0446−0.15910.149*
C110.75714 (9)0.7719 (2)0.12926 (10)0.0424 (4)
C120.79167 (12)0.4373 (3)0.16850 (11)0.0580 (5)
H120.80390.41940.11000.070*
C130.78506 (12)0.3050 (3)0.31347 (11)0.0584 (5)
H13A0.72810.31090.32050.070*
H13B0.80800.43560.33570.070*
C140.81906 (16)0.1190 (4)0.36122 (14)0.0812 (7)
H14A0.7993−0.00940.33530.122*
H14B0.80400.12480.42140.122*
H14C0.87580.12190.35780.122*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0601 (3)0.0926 (4)0.0674 (3)−0.0200 (3)0.0024 (2)−0.0204 (3)
O10.0478 (7)0.0593 (7)0.0647 (7)0.0024 (5)0.0108 (6)0.0029 (6)
O20.0658 (9)0.0824 (10)0.0985 (11)0.0239 (8)0.0096 (8)0.0267 (9)
O30.0954 (10)0.0428 (7)0.0519 (7)0.0049 (6)0.0048 (7)0.0053 (5)
N10.0510 (8)0.0480 (8)0.0687 (9)−0.0032 (7)−0.0003 (7)0.0059 (7)
N20.0445 (7)0.0411 (7)0.0464 (7)−0.0041 (6)−0.0016 (6)0.0019 (6)
N30.0495 (8)0.0455 (8)0.0546 (8)−0.0002 (6)−0.0009 (6)0.0080 (6)
N40.0477 (8)0.0475 (8)0.0529 (8)−0.0023 (6)−0.0001 (6)0.0067 (6)
N50.0504 (8)0.0442 (8)0.0461 (7)−0.0011 (6)−0.0046 (6)0.0045 (6)
C10.0440 (9)0.0595 (10)0.0409 (8)−0.0040 (7)0.0085 (7)−0.0054 (7)
C20.0475 (10)0.0673 (12)0.0596 (10)0.0089 (8)−0.0050 (8)0.0090 (9)
C30.0537 (10)0.0448 (9)0.0652 (11)0.0078 (8)0.0022 (8)0.0091 (8)
C40.0437 (8)0.0440 (8)0.0391 (8)0.0033 (7)0.0078 (6)0.0001 (7)
C50.0482 (9)0.0501 (10)0.0620 (10)0.0016 (8)−0.0058 (8)0.0132 (8)
C60.0540 (10)0.0485 (9)0.0490 (9)−0.0009 (8)0.0061 (7)−0.0045 (7)
C70.0437 (9)0.0413 (8)0.0476 (9)−0.0043 (7)−0.0045 (7)0.0016 (7)
C80.0461 (9)0.0477 (9)0.0607 (10)−0.0032 (7)−0.0022 (8)0.0003 (8)
C90.0483 (10)0.0690 (12)0.0859 (14)0.0012 (9)0.0135 (10)−0.0138 (11)
C100.0811 (16)0.127 (2)0.0917 (17)0.0149 (16)0.0392 (14)0.0044 (16)
C110.0437 (8)0.0391 (8)0.0441 (8)−0.0044 (7)−0.0070 (7)−0.0013 (7)
C120.0857 (13)0.0450 (10)0.0434 (9)−0.0065 (9)0.0000 (9)0.0018 (8)
C130.0672 (12)0.0585 (11)0.0494 (9)0.0055 (9)0.0033 (8)0.0074 (8)
C140.1104 (18)0.0668 (13)0.0665 (13)0.0154 (12)0.0013 (12)0.0190 (11)

Geometric parameters (Å, °)

Cl1—C11.7462 (17)C4—C51.376 (2)
O1—C81.331 (2)C4—C61.511 (2)
O1—C91.463 (2)C5—H50.9300
O2—C81.205 (2)C6—H6A0.9700
O3—C121.322 (2)C6—H6B0.9700
O3—C131.450 (2)C7—C111.391 (2)
N1—C11.316 (2)C7—C81.468 (2)
N1—C51.336 (2)C9—C101.489 (3)
N2—C111.348 (2)C9—H9A0.9700
N2—N31.3579 (18)C9—H9B0.9700
N2—C61.463 (2)C10—H10A0.9600
N3—N41.3103 (19)C10—H10B0.9600
N4—C71.366 (2)C10—H10C0.9600
N5—C121.264 (2)C12—H120.9300
N5—C111.387 (2)C13—C141.493 (3)
C1—C21.371 (3)C13—H13A0.9700
C2—C31.378 (3)C13—H13B0.9700
C2—H20.9300C14—H14A0.9600
C3—C41.378 (2)C14—H14B0.9600
C3—H30.9300C14—H14C0.9600
C8—O1—C9115.82 (15)O2—C8—O1123.82 (16)
C12—O3—C13117.92 (14)O2—C8—C7123.34 (17)
C1—N1—C5115.93 (15)O1—C8—C7112.83 (15)
C11—N2—N3111.41 (13)O1—C9—C10107.54 (18)
C11—N2—C6128.15 (13)O1—C9—H9A110.2
N3—N2—C6120.40 (13)C10—C9—H9A110.2
N4—N3—N2107.16 (13)O1—C9—H9B110.2
N3—N4—C7109.08 (13)C10—C9—H9B110.2
C12—N5—C11117.65 (14)H9A—C9—H9B108.5
N1—C1—C2125.22 (16)C9—C10—H10A109.5
N1—C1—Cl1115.20 (13)C9—C10—H10B109.5
C2—C1—Cl1119.57 (14)H10A—C10—H10B109.5
C1—C2—C3117.28 (16)C9—C10—H10C109.5
C1—C2—H2121.4H10A—C10—H10C109.5
C3—C2—H2121.4H10B—C10—H10C109.5
C4—C3—C2119.84 (16)N2—C11—N5119.02 (14)
C4—C3—H3120.1N2—C11—C7103.90 (13)
C2—C3—H3120.1N5—C11—C7137.02 (15)
C5—C4—C3117.18 (16)N5—C12—O3123.85 (16)
C5—C4—C6121.16 (15)N5—C12—H12118.1
C3—C4—C6121.65 (15)O3—C12—H12118.1
N1—C5—C4124.54 (16)O3—C13—C14106.49 (16)
N1—C5—H5117.7O3—C13—H13A110.4
C4—C5—H5117.7C14—C13—H13A110.4
N2—C6—C4112.19 (13)O3—C13—H13B110.4
N2—C6—H6A109.2C14—C13—H13B110.4
C4—C6—H6A109.2H13A—C13—H13B108.6
N2—C6—H6B109.2C13—C14—H14A109.5
C4—C6—H6B109.2C13—C14—H14B109.5
H6A—C6—H6B107.9H14A—C14—H14B109.5
N4—C7—C11108.44 (14)C13—C14—H14C109.5
N4—C7—C8123.09 (14)H14A—C14—H14C109.5
C11—C7—C8128.35 (15)H14B—C14—H14C109.5
C11—N2—N3—N4−0.55 (17)C9—O1—C8—C7−179.47 (14)
C6—N2—N3—N4−178.53 (13)N4—C7—C8—O2169.02 (17)
N2—N3—N4—C70.30 (17)C11—C7—C8—O2−6.6 (3)
C5—N1—C1—C20.0 (3)N4—C7—C8—O1−10.2 (2)
C5—N1—C1—Cl1−179.06 (13)C11—C7—C8—O1174.16 (15)
N1—C1—C2—C30.0 (3)C8—O1—C9—C10175.16 (19)
Cl1—C1—C2—C3179.07 (13)N3—N2—C11—N5178.28 (13)
C1—C2—C3—C40.2 (3)C6—N2—C11—N5−3.9 (2)
C2—C3—C4—C5−0.4 (2)N3—N2—C11—C70.55 (17)
C2—C3—C4—C6178.87 (15)C6—N2—C11—C7178.34 (14)
C1—N1—C5—C4−0.3 (3)C12—N5—C11—N2144.61 (16)
C3—C4—C5—N10.4 (3)C12—N5—C11—C7−38.6 (3)
C6—C4—C5—N1−178.81 (16)N4—C7—C11—N2−0.36 (17)
C11—N2—C6—C4−88.86 (19)C8—C7—C11—N2175.79 (15)
N3—N2—C6—C488.75 (17)N4—C7—C11—N5−177.45 (17)
C5—C4—C6—N285.12 (19)C8—C7—C11—N5−1.3 (3)
C3—C4—C6—N2−94.08 (18)C11—N5—C12—O3177.40 (16)
N3—N4—C7—C110.04 (18)C13—O3—C12—N5−0.1 (3)
N3—N4—C7—C8−176.36 (15)C12—O3—C13—C14−169.17 (18)
C9—O1—C8—O21.3 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···N3i0.932.573.488 (2)167
C9—H9A···O2ii0.972.533.246 (3)131
C12—H12···O20.932.442.924 (3)112

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2675).

References

  • Banks, B. J. & Chubb, N. A. L. (1999a). Eur. Patent 957 094.
  • Banks, B. J. & Chubb, N. A. L. (1999b). Chem. Abstr 131, 337025.
  • Bruker (2000). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, W., Chen, Q., Wu, Q. Y. & Yang, G. F. (2005). Chin. J. Org. Chem.25, 1477–1481.
  • Chen, X. B. & Shi, D. Q. (2008). J. Heterocycl. Chem.45, 1493–1497.
  • Liu, Z. M., Yang, G. F. & Qing, X. H. (2001). J. Chem. Technol. Biotechnol.76, 1154–1158.
  • Najim, A. A., Yaseen, A. A. & Asmehan, A. (2004). Heteroatom. Chem.15, 380–387.
  • Ogura, T., Numata, A., Ueno, H. & Masuzawa, Y. (2000a). World Patent 0 039 106.
  • Ogura, T., Numata, A., Ueno, H. & Masuzawa, Y. (2000b). Chem. Abstr.133, 74023.
  • Sasada, Y. (1984). Molecular and Crystal Structures in Chemistry Handbook, 3rd ed. Tokyo: The Chemical Society of Japan, Maruzen.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Shuto, A., Kisida, H., Tsuchiya, T., Takada, Y. & Fujimoto, H. (1995a). World Patent 9 529 175.
  • Shuto, A., Kisida, H., Tsuchiya, T., Takada, Y. & Fujimoto, H. (1995b). Chem. Abstr 124, 176136.
  • Wang, Z., Jian, F., Duan, C., Bai, Z. & You, X. (1998). Acta Cryst. C54, 1927–1929.
  • Yuan, J. Z., Fu, B. Q., Ding, M. W. & Yang, G.-F. (2006). Eur. J. Org. Chem.18, 4170–4176.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography