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

Prabakaran, K.; Hathwar, V.R.; Maiyalagan, T.; Kirthana, M.V.; Khan, F.N.

doi:10.1107/S1600536809024829

organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1752

doi:10.1107/S1600536809024829

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

K. Prabakaran,^a Venkatesha R. Hathwar,^b T. Maiyalagan,^a M. V. Kirthana ^a and F. Nawaz Khan ^a ^*

^aChemistry Division, School of Science and Humanities, VIT University, Vellore 632 014, Tamil Nadu, India, and ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India
^*Correspondence e-mail: nawaz_f@yahoo.co.in

(Received 16 June 2009; accepted 27 June 2009; online 4 July 2009)

In the title compound, C₅H₇N₃O₂, all non-H atoms lie in a common plane, with a maximum deviation of 0.061 (2)° for the ester methyl C atom. The structure is stabilized by intermolecular C—H⋯O hydrogen bonds.

Related literature

For general background to the applications of triazoles and their derivatives, see: Abu-Orabi et al. (1989 ); Fan & Katritzky (1996 ); Dehne (1994 ); Wang et al. (1998 ). For a related structure, see: Prabakaran et al. (2009 ).

Experimental

Crystal data

C₅H₇N₃O₂
M_r = 141.14
Monoclinic, P 2₁ /c
a = 3.9482 (10) Å
b = 7.9549 (15) Å
c = 21.655 (4) Å
β = 92.05 (2)°
V = 679.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 290 K
0.30 × 0.20 × 0.10 mm

Data collection

Oxford Xcalibur Eos(Nova) CCD detector diffractometer
Absorption correction: multi-scan (CrysAlisPro RED; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlisPro CCD and CrysAlisPro RED, including ABSPACK. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.926, T_max = 0.989
7464 measured reflections
1262 independent reflections
910 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.119
S = 1.07
1262 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1ⁱ	0.93	2.53	3.416 (3)	159
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlisPro CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlisPro CCD and CrysAlisPro RED, including ABSPACK. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlisPro CCD; data reduction: CrysAlisPro RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlisPro CCD and CrysAlisPro RED, including ABSPACK. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and CAMERON (Watkin et al., 1993 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024829/bt2973sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024829/bt2973Isup2.hkl

checkCIF report

Comment top

Triazoles and their derivatives find their application in pharmaceuticals, agrochemicals, dyes, photographic materials, and in corrosion inhibition (Fan & Katritzky, 1996; Dehne,1994; Abu-Orabi et al., 1989). In continuous of our earlier report (Prabakaran et al., 2009), here the crystal structure of the title compound is presented. All non-H atoms lie in a common plane with maximum deviation of 0.061 (2)° for atom C4. The packing is stabilized by C—H···O hydrogen bonds.

Related literature top

For general background to the applications of triazoles and their derivatives, see: Abu-Orabi et al. (1989); Fan & Katritzky (1996); Dehne (1994); Wang et al. (1998). For a related structure, see: Prabakaran et al. (2009).

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 K_2CO3 (1.3 g), metyliodide (ml), the mixture was then stirred at 273 K for 1hr, 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. A portion of the mixture was also analysed by HPLC analysis and also isolated by preparative HPLC techniques. The single crystal of the title compound for X-ray structure anlaysis was obtained from ether solution by slow evaporation.

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 (Farrugia, 1999) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. ORTEP diagram of the asymmetric unit of (I) with 50% probability displacement ellipsoids.

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

Crystal data top

C₅H₇N₃O₂	F(000) = 296
M_r = 141.14	D_x = 1.379 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 783 reflections
a = 3.9482 (10) Å	θ = 2.0–21.4°
b = 7.9549 (15) Å	µ = 0.11 mm⁻¹
c = 21.655 (4) Å	T = 290 K
β = 92.05 (2)°	Plate, colorless
V = 679.7 (2) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Oxford Xcalibur Eos(Nova) CCD detector diffractometer	1262 independent reflections
Radiation source: Enhance (Mo) X-ray Source	910 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
ω scans	θ_max = 25.5°, θ_min = 3.2°
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)	h = −4→4
T_min = 0.926, T_max = 0.989	k = −9→9
7464 measured reflections	l = −26→26

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0589P)² + 0.0659P] where P = (F_o² + 2F_c²)/3
1262 reflections	(Δ/σ)_max < 0.001
93 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₅H₇N₃O₂	V = 679.7 (2) Å³
M_r = 141.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.9482 (10) Å	µ = 0.11 mm⁻¹
b = 7.9549 (15) Å	T = 290 K
c = 21.655 (4) Å	0.30 × 0.20 × 0.10 mm
β = 92.05 (2)°

Data collection top

Oxford Xcalibur Eos(Nova) CCD detector diffractometer	1262 independent reflections
Absorption correction: multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)	910 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.989	R_int = 0.043
7464 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.07	Δρ_max = 0.19 e Å⁻³
1262 reflections	Δρ_min = −0.17 e Å⁻³
93 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.

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

	x	y	z	U_iso*/U_eq
N1	0.2453 (4)	0.56849 (18)	0.43005 (7)	0.0442 (4)
N2	0.3338 (4)	0.71794 (19)	0.45090 (7)	0.0449 (4)
N3	0.4803 (5)	0.8185 (2)	0.41047 (7)	0.0562 (5)
O1	0.3755 (4)	0.42664 (18)	0.27655 (6)	0.0620 (5)
O2	0.1319 (4)	0.29948 (17)	0.35597 (6)	0.0539 (4)
C1	0.4849 (6)	0.7258 (2)	0.35967 (9)	0.0547 (6)
H1	0.5707	0.7596	0.3222	0.066*
C2	0.3408 (5)	0.5700 (2)	0.37131 (8)	0.0407 (5)
C3	0.2884 (5)	0.4274 (2)	0.32930 (8)	0.0435 (5)
C4	0.0524 (6)	0.1556 (3)	0.31750 (10)	0.0634 (6)
H4A	−0.0937	0.1895	0.2834	0.095*
H4B	−0.0597	0.0720	0.3414	0.095*
H4C	0.2579	0.1095	0.3022	0.095*
C5	0.2690 (6)	0.7700 (3)	0.51385 (9)	0.0567 (6)
H5A	0.1463	0.6831	0.5342	0.085*
H5B	0.1374	0.8715	0.5130	0.085*
H5C	0.4805	0.7896	0.5359	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0534 (11)	0.0371 (9)	0.0423 (9)	−0.0034 (7)	0.0041 (7)	0.0000 (7)
N2	0.0581 (11)	0.0348 (9)	0.0419 (9)	−0.0033 (7)	0.0029 (7)	−0.0004 (7)
N3	0.0755 (13)	0.0424 (10)	0.0511 (10)	−0.0100 (9)	0.0069 (9)	0.0050 (8)
O1	0.0904 (12)	0.0553 (9)	0.0413 (8)	0.0058 (8)	0.0164 (7)	0.0007 (6)
O2	0.0715 (10)	0.0457 (8)	0.0450 (8)	−0.0120 (7)	0.0066 (6)	−0.0058 (6)
C1	0.0740 (15)	0.0480 (12)	0.0427 (11)	−0.0060 (10)	0.0109 (10)	0.0065 (9)
C2	0.0454 (11)	0.0381 (10)	0.0388 (10)	0.0017 (8)	0.0034 (8)	0.0050 (8)
C3	0.0502 (12)	0.0422 (11)	0.0382 (10)	0.0072 (9)	0.0018 (8)	0.0038 (8)
C4	0.0752 (16)	0.0449 (12)	0.0699 (15)	−0.0064 (11)	0.0016 (12)	−0.0155 (10)
C5	0.0770 (16)	0.0479 (13)	0.0455 (11)	−0.0022 (10)	0.0067 (10)	−0.0084 (9)

Geometric parameters (Å, º) top

N1—N2	1.315 (2)	C1—H1	0.9300
N1—C2	1.340 (2)	C2—C3	1.464 (3)
N2—N3	1.333 (2)	C4—H4A	0.9600
N2—C5	1.456 (2)	C4—H4B	0.9600
N3—C1	1.325 (2)	C4—H4C	0.9600
O1—C3	1.205 (2)	C5—H5A	0.9600
O2—C3	1.333 (2)	C5—H5B	0.9600
O2—C4	1.444 (2)	C5—H5C	0.9600
C1—C2	1.391 (3)

N2—N1—C2	103.75 (15)	O2—C3—C2	112.31 (16)
N1—N2—N3	115.69 (15)	O2—C4—H4A	109.5
N1—N2—C5	121.67 (15)	O2—C4—H4B	109.5
N3—N2—C5	122.63 (16)	H4A—C4—H4B	109.5
C1—N3—N2	103.33 (16)	O2—C4—H4C	109.5
C3—O2—C4	116.74 (16)	H4A—C4—H4C	109.5
N3—C1—C2	109.13 (17)	H4B—C4—H4C	109.5
N3—C1—H1	125.4	N2—C5—H5A	109.5
C2—C1—H1	125.4	N2—C5—H5B	109.5
N1—C2—C1	108.10 (16)	H5A—C5—H5B	109.5
N1—C2—C3	123.02 (17)	N2—C5—H5C	109.5
C1—C2—C3	128.88 (17)	H5A—C5—H5C	109.5
O1—C3—O2	124.03 (17)	H5B—C5—H5C	109.5
O1—C3—C2	123.65 (18)

C2—N1—N2—N3	0.1 (2)	N3—C1—C2—C3	179.47 (18)
C2—N1—N2—C5	179.01 (17)	C4—O2—C3—O1	−2.7 (3)
N1—N2—N3—C1	0.2 (2)	C4—O2—C3—C2	176.96 (16)
C5—N2—N3—C1	−178.75 (18)	N1—C2—C3—O1	−179.38 (18)
N2—N3—C1—C2	−0.3 (2)	C1—C2—C3—O1	1.7 (3)
N2—N1—C2—C1	−0.3 (2)	N1—C2—C3—O2	1.0 (3)
N2—N1—C2—C3	−179.42 (17)	C1—C2—C3—O2	−177.96 (19)
N3—C1—C2—N1	0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.53	3.416 (3)	159

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₅H₇N₃O₂
M_r	141.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	3.9482 (10), 7.9549 (15), 21.655 (4)
β (°)	92.05 (2)
V (Å³)	679.7 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Oxford Xcalibur Eos(Nova) CCD detector diffractometer
Absorption correction	Multi-scan (CrysAlis PRO RED; Oxford Diffraction, 2009)
T_min, T_max	0.926, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	7464, 1262, 910
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.119, 1.07
No. of reflections	1262
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.17

Computer programs: CrysAlis PRO CCD (Oxford Diffraction, 2009), CrysAlis PRO RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1999) and CAMERON (Watkin et al., 1993), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.9300	2.5300	3.416 (3)	159.00

Symmetry code: (i) −x+1, y+1/2, −z+1/2.

Acknowledgements

We thank the Department of Science and Technology, India, for use of the CCD facility setup under the IRHPA–DST program at IISc. We thank Professor T. N. Guru Row, IISc, Bangalore, for useful crystallographic discussions. FNK thanks the DST for Fast Track Proposal funding.

References

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