Methyl 1-methyl-1H-1,2,3-triazole-4-carboxyl­ate

Khan, F.N.; Prabakaran, K.; Roopan, S.M.; Hathwar, V.R.; Akkurt, M.

doi:10.1107/S1600536810019173

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1468

https://doi.org/10.1107/S1600536810019173

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Methyl 1-methyl-1H-1,2,3-triazole-4-carboxylate

F. Nawaz Khan,^a K. Prabakaran,^a S. Mohana Roopan,^a Venkatesha R. Hathwar ^b and Mehmet Akkurt ^c ^*

^aOrganic and Medicinal Chemistry Research Laboratory, Organic Chemistry Division, School of Advanced Sciences, VIT University, Vellore 632 014, Tamil Nadu, India, ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India, and ^cDepartment of Physics, Faculty of Arts and Sciences, Erciyes University, 38039 Kayseri, Turkey
^*Correspondence e-mail: akkurt@erciyes.edu.tr

(Received 18 May 2010; accepted 21 May 2010; online 26 May 2010)

The title molecule, C₅H₇N₃O₂, has an almost planar conformation, with a maximum deviation of 0.043 (3) Å, except for the methyl H atoms. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules into layers parallel to the bc plane. Intermolecular π–π stacking interactions [centroid–centroid distances = 3.685 (2) and 3.697 (2) Å] are observed between the parallel triazole rings.

Related literature

For related structures, see: Prabakaran et al. (2009a ,b ); Beitelman et al. (2007 ); Jabli et al. (2010 ). For the properties and applications of related compounds, see: Dehne (1994 ); Fan & Katritzky (1996 ); Genin et al. (2000 ); Velazquez et al. (1998 ).

Experimental

Crystal data

C₅H₇N₃O₂
M_r = 141.14
Triclinic, $[P \overline 1]$
a = 5.697 (1) Å
b = 7.1314 (11) Å
c = 8.6825 (16) Å
α = 71.053 (16)°
β = 86.865 (15)°
γ = 76.528 (14)°
V = 324.37 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.15 × 0.10 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur Eos (Nova) CCD detector diffractometer
6915 measured reflections
1108 independent reflections
800 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.173
S = 1.13
1108 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1ⁱ	0.96	2.59	3.509 (5)	160
C5—H5B⋯O1ⁱⁱ	0.96	2.39	3.277 (5)	153
Symmetry codes: (i) x, y, z+1; (ii) x-1, y, z.

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO CCD and CrysAlis PRO RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO CCD; data reduction: CrysAlis PRO RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO CCD and CrysAlis PRO RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810019173/xu2764sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810019173/xu2764Isup2.hkl

checkCIF report

Comment top

1,2,3-Triazoles are useful synthetic targets in organic synthesis and are associated with biological properties such as antiviral, antibacterial, antiepileptic and antiallergic (Velazquez et al., 1998; Genin et al., 2000). They have also found applications as agrochemicals, dyes, hotographic materials, and in corrosion inhibition (Fan & Katritzky, 1996; Dehne, 1994). In continuous of our earlier reports (Prabakaran et al., 2009a,b), here the crystal structure of the title compound is presented.

As shown in Fig. 1, the conformation of the title molecule is almost planar, with a maximum deviation of -0.043 (3) Å for O1, except the H atoms of two methyl groups.

In the crystal structure, molecules connect to each other, via the intermolecular C—H···O hydrogen bonds (Table 1, Fig. 2), into two-dimensional layers parallel to the bc plane, and intermolecular π–π stacking interactions [Cg1···Cg1(1 - x, -y, 2 - z) = 3.685 (2) Å and Cg1···Cg1(1 - x, 1 - y, 2 - z) = 3.697 (2) Å, where Cg1 is a centroid of the triazole ring] between the parallel triazole rings contribute to the stabilization of the structure.

Related literature top

For related structures, see: Prabakaran et al. (2009a,b); Beitelman et al. (2007); Jabli et al. (2010). For the properties and applications of related compounds, see: Dehne (1994); Fan & Katritzky (1996); Genin et al. (2000); Velazquez et al. (1998).

Experimental top

To methyl 1H-1,2,3-triazole-4-carboxylate (2 g) in dry DMF (15 ml) maintained at 273 K in nitrogen atmosphere, was added K₂CO₃ (1.3 g), methyliodide (0.98 ml), the mixture was then stirred at 273 K for 1 h, allowed to warm to room temperature and stirred till completion of reaction, monitored by TLC. The reaction mixture on LCMS analysis showed three isomers well separated with their significant retention time and high purity. Three fractions were identified by mass spectroscopy. The solvent was evaporated under vacuo and the residue was isolated into individual isomers by column chromatography. The single crystals of the title compound for X-ray structure analysis were obtained from ether solution by slow evaporation.

Structure description top

As shown in Fig. 1, the conformation of the title molecule is almost planar, with a maximum deviation of -0.043 (3) Å for O1, except the H atoms of two methyl groups.

For related structures, see: Prabakaran et al. (2009a,b); Beitelman et al. (2007); Jabli et al. (2010). For the properties and applications of related compounds, see: Dehne (1994); Fan & Katritzky (1996); Genin et al. (2000); Velazquez et al. (1998).

Computing details top

Data collection: CrysAlis PRO CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO CCD (Oxford Diffraction, 2009); data reduction: CrysAlis PRO RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The title molecule showing the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. View of the crystal packing of (I), viewed down the a axis. The H atoms not involved in the hydrogen bonding pattern have been omitted for clarity.

Methyl 1-methyl-1H-1,2,3-triazole-4-carboxylate top

Crystal data top

C₅H₇N₃O₂	Z = 2
M_r = 141.14	F(000) = 148
Triclinic, P1	D_x = 1.445 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.697 (1) Å	Cell parameters from 1326 reflections
b = 7.1314 (11) Å	θ = 2.0–20.7°
c = 8.6825 (16) Å	µ = 0.11 mm⁻¹
α = 71.053 (16)°	T = 293 K
β = 86.865 (15)°	Block, colourless
γ = 76.528 (14)°	0.15 × 0.10 × 0.05 mm
V = 324.37 (10) Å³

Data collection top

Oxford Xcalibur Eos (Nova) CCD detector diffractometer	800 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.049
Graphite monochromator	θ_max = 25.0°, θ_min = 3.1°
ω scans	h = −6→6
6915 measured reflections	k = −8→8
1108 independent reflections	l = −10→10

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0741P)² + 0.2349P] where P = (F_o² + 2F_c²)/3
1108 reflections	(Δ/σ)_max < 0.001
93 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₅H₇N₃O₂	γ = 76.528 (14)°
M_r = 141.14	V = 324.37 (10) Å³
Triclinic, P1	Z = 2
a = 5.697 (1) Å	Mo Kα radiation
b = 7.1314 (11) Å	µ = 0.11 mm⁻¹
c = 8.6825 (16) Å	T = 293 K
α = 71.053 (16)°	0.15 × 0.10 × 0.05 mm
β = 86.865 (15)°

Data collection top

Oxford Xcalibur Eos (Nova) CCD detector diffractometer	800 reflections with I > 2σ(I)
6915 measured reflections	R_int = 0.049
1108 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.173	H-atom parameters constrained
S = 1.13	Δρ_max = 0.26 e Å⁻³
1108 reflections	Δρ_min = −0.23 e Å⁻³
93 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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
O1	0.6694 (5)	0.2352 (5)	0.5832 (3)	0.0591 (13)
O2	0.2797 (4)	0.2639 (4)	0.6475 (3)	0.0440 (9)
N1	0.7108 (5)	0.2390 (4)	1.0644 (3)	0.0361 (10)
N2	0.4740 (5)	0.2478 (5)	1.0897 (4)	0.0430 (11)
N3	0.3757 (5)	0.2534 (5)	0.9553 (4)	0.0417 (10)
C1	0.8687 (7)	0.2325 (6)	1.1941 (5)	0.0471 (14)
C2	0.7651 (6)	0.2415 (5)	0.9131 (4)	0.0369 (11)
C3	0.5521 (6)	0.2492 (5)	0.8434 (4)	0.0342 (11)
C4	0.5106 (6)	0.2486 (5)	0.6793 (4)	0.0373 (12)
C5	0.2257 (7)	0.2676 (7)	0.4852 (5)	0.0532 (14)
H1A	0.77460	0.24230	1.28750	0.0700*
H1B	0.94680	0.34440	1.15670	0.0700*
H1C	0.98850	0.10660	1.22340	0.0700*
H2	0.91520	0.23860	0.86500	0.0440*
H5A	0.26750	0.38410	0.40620	0.0790*
H5B	0.05650	0.27540	0.47490	0.0790*
H5C	0.31730	0.14580	0.46690	0.0790*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0354 (15)	0.103 (3)	0.0513 (18)	−0.0203 (15)	0.0119 (13)	−0.0399 (17)
O2	0.0336 (14)	0.0667 (18)	0.0370 (15)	−0.0139 (12)	−0.0013 (11)	−0.0216 (13)
N1	0.0315 (16)	0.0468 (19)	0.0314 (17)	−0.0104 (13)	0.0007 (13)	−0.0133 (13)
N2	0.0346 (17)	0.057 (2)	0.0386 (18)	−0.0098 (14)	0.0038 (14)	−0.0178 (15)
N3	0.0348 (16)	0.055 (2)	0.0354 (18)	−0.0108 (14)	0.0002 (14)	−0.0140 (14)
C1	0.045 (2)	0.062 (3)	0.036 (2)	−0.0133 (19)	−0.0046 (17)	−0.0165 (19)
C2	0.0306 (18)	0.047 (2)	0.036 (2)	−0.0126 (16)	0.0054 (15)	−0.0155 (17)
C3	0.0286 (18)	0.038 (2)	0.039 (2)	−0.0116 (15)	0.0068 (15)	−0.0144 (16)
C4	0.038 (2)	0.039 (2)	0.038 (2)	−0.0120 (16)	−0.0022 (18)	−0.0137 (17)
C5	0.046 (2)	0.082 (3)	0.040 (2)	−0.025 (2)	−0.0030 (18)	−0.023 (2)

Geometric parameters (Å, º) top

O1—C4	1.205 (4)	C3—C4	1.459 (5)
O2—C4	1.331 (4)	C1—H1A	0.9600
O2—C5	1.449 (5)	C1—H1B	0.9600
N1—N2	1.345 (4)	C1—H1C	0.9600
N1—C1	1.462 (5)	C2—H2	0.9300
N1—C2	1.328 (4)	C5—H5A	0.9600
N2—N3	1.307 (5)	C5—H5B	0.9600
N3—C3	1.361 (5)	C5—H5C	0.9600
C2—C3	1.367 (5)

O1···C5ⁱ	3.277 (5)	C4···N2^vii	3.439 (5)
O2···N3	2.731 (4)	C5···C1^x	3.435 (6)
O1···H1Aⁱⁱ	2.5900	C5···O1^vi	3.277 (5)
O1···H5A	2.6300	C1···H5B^ix	2.8500
O1···H5Bⁱ	2.3900	C4···H5A^iv	3.0300
O1···H5C	2.5900	H1A···O1^xi	2.5900
O1···H1Cⁱⁱⁱ	2.8400	H1A···H5B^ix	2.4500
O1···H5A^iv	2.8500	H1B···N3^viii	2.9100
O1···H5C^v	2.8700	H1C···O1ⁱⁱⁱ	2.8400
O1···H2	2.8900	H2···O1	2.8900
O2···H2^vi	2.7300	H2···O2ⁱ	2.7300
N2···C3^vii	3.438 (5)	H2···N3ⁱ	2.8100
N2···C4^vii	3.439 (5)	H5A···O1	2.6300
N3···O2	2.731 (4)	H5A···O1^iv	2.8500
N3···C1^viii	3.434 (6)	H5A···C4^iv	3.0300
N3···C3^vii	3.376 (5)	H5B···O1^vi	2.3900
N3···H2^vi	2.8100	H5B···C1^x	2.8500
N3···H1B^viii	2.9100	H5B···H1A^x	2.4500
C1···C5^ix	3.435 (6)	H5C···O1	2.5900
C1···N3^viii	3.434 (6)	H5C···O1^v	2.8700
C3···N3^vii	3.376 (5)	H5C···H5C^v	2.5200
C3···N2^vii	3.438 (5)

C4—O2—C5	115.6 (3)	N1—C1—H1B	109.00
N2—N1—C1	120.4 (3)	N1—C1—H1C	110.00
N2—N1—C2	110.7 (3)	H1A—C1—H1B	109.00
C1—N1—C2	129.0 (3)	H1A—C1—H1C	109.00
N1—N2—N3	107.9 (3)	H1B—C1—H1C	109.00
N2—N3—C3	107.9 (3)	N1—C2—H2	128.00
N1—C2—C3	105.0 (3)	C3—C2—H2	127.00
N3—C3—C2	108.6 (3)	O2—C5—H5A	109.00
N3—C3—C4	123.5 (3)	O2—C5—H5B	109.00
C2—C3—C4	127.9 (3)	O2—C5—H5C	110.00
O1—C4—O2	123.8 (3)	H5A—C5—H5B	109.00
O1—C4—C3	123.3 (3)	H5A—C5—H5C	109.00
O2—C4—C3	112.9 (3)	H5B—C5—H5C	109.00
N1—C1—H1A	109.00

C5—O2—C4—O1	−1.1 (6)	N2—N3—C3—C4	178.5 (3)
C5—O2—C4—C3	179.0 (3)	N1—C2—C3—N3	0.7 (4)
C1—N1—N2—N3	179.6 (3)	N1—C2—C3—C4	−178.0 (3)
C2—N1—N2—N3	0.8 (4)	N3—C3—C4—O1	−176.4 (4)
N2—N1—C2—C3	−0.9 (4)	N3—C3—C4—O2	3.5 (5)
C1—N1—C2—C3	−179.6 (4)	C2—C3—C4—O1	2.1 (6)
N1—N2—N3—C3	−0.3 (4)	C2—C3—C4—O2	−178.0 (4)
N2—N3—C3—C2	−0.2 (4)

Symmetry codes: (i) x+1, y, z; (ii) x, y, z−1; (iii) −x+2, −y, −z+2; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y, −z+1; (vi) x−1, y, z; (vii) −x+1, −y, −z+2; (viii) −x+1, −y+1, −z+2; (ix) x+1, y, z+1; (x) x−1, y, z−1; (xi) x, y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1^xi	0.96	2.59	3.509 (5)	160
C5—H5B···O1^vi	0.96	2.39	3.277 (5)	153

Symmetry codes: (vi) x−1, y, z; (xi) x, y, z+1.

Experimental details

Crystal data
Chemical formula	C₅H₇N₃O₂
M_r	141.14
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.697 (1), 7.1314 (11), 8.6825 (16)
α, β, γ (°)	71.053 (16), 86.865 (15), 76.528 (14)
V (Å³)	324.37 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.15 × 0.10 × 0.05

Data collection
Diffractometer	Oxford Xcalibur Eos (Nova) CCD detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6915, 1108, 800
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.173, 1.13
No. of reflections	1108
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.23

Computer programs: CrysAlis PRO CCD (Oxford Diffraction, 2009), CrysAlis PRO RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱ	0.96	2.59	3.509 (5)	160
C5—H5B···O1ⁱⁱ	0.96	2.39	3.277 (5)	153

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

Acknowledgements

We thank the Department of Science and Technology, India, for use of the CCD facility set up under the IRHPA–DST program at IISc. We thank Professor T. N. Guru Row, IISc, Bangalore, for the data collection. F·NK thanks the DST for Fast Track Proposal funding.

References

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