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

Prabakaran, K.; Maiyalagan, T.; Hathwar, V.R.; Kazak, C.; Khan, F.N.

doi:10.1107/S1600536809000877

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o300

doi:10.1107/S1600536809000877

Open

access

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

K. Prabakaran,^a T. Maiyalagan,^a Venkatesha R. Hathwar,^b Canan Kazak ^c and F. Nawaz Khan ^a ^*

^aChemistry Division, School of Science and Humanities, VIT University, Vellore 632 014, Tamil Nadu, India, ^bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, Karnataka, India, and ^cOndokuz Mayıs University, Arts and Sciences Faculty, Department of Physics, 55139 Samsun, Turkey
^*Correspondence e-mail: nawaz_f@yahoo.co.in

(Received 6 January 2009; accepted 8 January 2009; online 14 January 2009)

The title compound, C₄H₅N₃O₂, features an essentially planar molecule (r.m.s. deviation for all non-H atoms = 0.013 Å). The crystal structure is stabilized by intermolecular N—H⋯O hydrogen bonds and π–π stacking interactions (centroid–centroid distance 3.882 Å).

Related literature

For general background, see: Abu-Orabi et al. (1989 ); Fan & Katritzky (1996 ); Dehne (1994 ). For a related structure, see: Wang et al. (1998 ).

Experimental

Crystal data

C₄H₅N₃O₂
M_r = 127.11
Monoclinic, P 2₁ /n
a = 3.8823 (7) Å
b = 17.499 (3) Å
c = 8.8171 (17) Å
β = 100.938 (3)°
V = 588.12 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 290 (2) K
0.30 × 0.23 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.956, T_max = 0.977
4285 measured reflections
1098 independent reflections
917 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.116
S = 1.06
1098 reflections
91 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯O1ⁱ	0.896 (19)	1.980 (19)	2.8659 (19)	169.56 (18)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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: PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000877/bt2847sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809000877/bt2847Isup2.hkl

checkCIF report

Comment top

Triazoles play an important role in pharmaceuticals, agrochemicals, dyes, photographic materials, and in corrosion inhibition (Fan & Katritzky, 1996; Dehne, 1994; Abu-Orabi et al., 1989).

The crystal structure of the title compound is stabilized by intermolecular N—H···O hydrogen bonds and π^···π stacking interactions between the triazole rings at (symmetry operator 1+X,Y,Z; centroid-centroid distance 3.882 Å).

Related literature top

For general background, see: Abu-Orabi et al. (1989); Fan & Katritzky (1996); Dehne (1994); Wang et al. (1998).

Experimental top

A mixture of methylpropiolate, 1 and trimethylsilylazide, 2 were heated at 100 °C till the completion of reaction, monitored by TLC. Then reaction mixture was cooled and methanol was added dropwise with cooling. The solid formed was allowed to stand for 30 min and filtered off, washed with ether, then with hexane. The product was then isolated as a colourless solid by column chromatography using 10% pet.ether/EtOAc. The single-crystal for X-ray structue anlaysis was obtained from ether solution by slow evaporation.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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: PLATON (Spek, 2003).

Figures top

	Fig. 1. ORTEP diagram of the asymmetric unit of the title compound with 50% probability displacement ellipsoids.
	Fig. 2. The crystal packing diagram of the title compound. The dotted lines indicate intermolecular N—H···O hydrogen bonds.

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

Crystal data top

C₄H₅N₃O₂	F(000) = 264
M_r = 127.11	D_x = 1.436 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1804 reflections
a = 3.8823 (7) Å	θ = 2.4–25.5°
b = 17.499 (3) Å	µ = 0.12 mm⁻¹
c = 8.8171 (17) Å	T = 290 K
β = 100.938 (3)°	Block, pale yellow
V = 588.12 (19) Å³	0.30 × 0.23 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1098 independent reflections
Radiation source: fine-focus sealed tube	917 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −4→4
T_min = 0.956, T_max = 0.977	k = −21→20
4285 measured 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0657P)² + 0.085P] where P = (F_o² + 2F_c²)/3
1098 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₄H₅N₃O₂	V = 588.12 (19) Å³
M_r = 127.11	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.8823 (7) Å	µ = 0.12 mm⁻¹
b = 17.499 (3) Å	T = 290 K
c = 8.8171 (17) Å	0.30 × 0.23 × 0.20 mm
β = 100.938 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1098 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	917 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.977	R_int = 0.016
4285 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.20 e Å⁻³
1098 reflections	Δρ_min = −0.12 e Å⁻³
91 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
H3N	0.668 (5)	0.1865 (11)	0.529 (2)	0.069 (6)*
H1	0.630 (5)	0.3213 (10)	0.510 (2)	0.067 (5)*
O1	0.2633 (4)	0.39888 (6)	0.89548 (14)	0.0672 (4)
O2	0.4220 (4)	0.44536 (7)	0.68279 (14)	0.0670 (4)
C3	0.3702 (4)	0.38941 (9)	0.77686 (18)	0.0502 (4)
N3	0.5970 (4)	0.21920 (8)	0.59504 (15)	0.0520 (4)
C2	0.4540 (4)	0.31459 (8)	0.71907 (16)	0.0440 (4)
N2	0.5029 (4)	0.19156 (8)	0.72315 (16)	0.0577 (4)
C1	0.5704 (4)	0.29447 (9)	0.58856 (18)	0.0495 (4)
N1	0.4149 (4)	0.25012 (7)	0.79947 (15)	0.0541 (4)
C4	0.3391 (8)	0.52244 (11)	0.7273 (3)	0.0937 (8)
H4A	0.0894	0.5296	0.7056	0.141*
H4B	0.4472	0.5590	0.6700	0.141*
H4C	0.4261	0.5295	0.8358	0.141*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0984 (10)	0.0524 (7)	0.0599 (8)	−0.0045 (6)	0.0379 (7)	−0.0077 (5)
O2	0.0959 (10)	0.0450 (7)	0.0671 (8)	0.0012 (6)	0.0330 (7)	0.0062 (5)
C3	0.0556 (9)	0.0481 (9)	0.0482 (9)	−0.0045 (7)	0.0137 (7)	−0.0012 (7)
N3	0.0643 (9)	0.0499 (8)	0.0443 (8)	0.0026 (6)	0.0167 (6)	−0.0038 (6)
C2	0.0478 (8)	0.0464 (8)	0.0384 (8)	−0.0034 (6)	0.0095 (6)	0.0015 (6)
N2	0.0754 (10)	0.0480 (8)	0.0532 (8)	0.0009 (6)	0.0213 (7)	0.0017 (6)
C1	0.0597 (10)	0.0499 (9)	0.0410 (9)	−0.0013 (7)	0.0152 (7)	0.0031 (7)
N1	0.0702 (9)	0.0480 (8)	0.0478 (8)	−0.0016 (6)	0.0207 (7)	0.0011 (5)
C4	0.134 (2)	0.0464 (11)	0.1117 (18)	0.0019 (11)	0.0499 (16)	0.0029 (11)

Geometric parameters (Å, º) top

O1—C3	1.2075 (19)	C2—N1	1.3561 (19)
O2—C3	1.3231 (19)	C2—C1	1.360 (2)
O2—C4	1.458 (2)	N2—N1	1.3065 (19)
C3—C2	1.464 (2)	C1—H1	0.906 (19)
N3—C1	1.322 (2)	C4—H4A	0.9600
N3—N2	1.3416 (19)	C4—H4B	0.9600
N3—H3N	0.90 (2)	C4—H4C	0.9600

C3—O2—C4	116.63 (15)	N3—C1—C2	104.91 (14)
O1—C3—O2	124.02 (15)	N3—C1—H1	121.4 (12)
O1—C3—C2	124.05 (14)	C2—C1—H1	133.7 (12)
O2—C3—C2	111.92 (13)	N2—N1—C2	108.49 (13)
C1—N3—N2	111.36 (14)	O2—C4—H4A	109.5
C1—N3—H3N	129.6 (12)	O2—C4—H4B	109.5
N2—N3—H3N	119.0 (12)	H4A—C4—H4B	109.5
N1—C2—C1	108.37 (14)	O2—C4—H4C	109.5
N1—C2—C3	120.51 (13)	H4A—C4—H4C	109.5
C1—C2—C3	131.12 (14)	H4B—C4—H4C	109.5
N1—N2—N3	106.88 (13)

C4—O2—C3—O1	−0.7 (3)	N2—N3—C1—C2	0.00 (17)
C4—O2—C3—C2	178.67 (17)	N1—C2—C1—N3	−0.01 (17)
O1—C3—C2—N1	−0.2 (2)	C3—C2—C1—N3	−179.24 (16)
O2—C3—C2—N1	−179.54 (14)	N3—N2—N1—C2	−0.03 (18)
O1—C3—C2—C1	178.95 (17)	C1—C2—N1—N2	0.03 (18)
O2—C3—C2—C1	−0.4 (2)	C3—C2—N1—N2	179.35 (13)
C1—N3—N2—N1	0.02 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O1ⁱ	0.896 (19)	1.980 (19)	2.8659 (19)	169.56 (18)

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

Experimental details

Crystal data
Chemical formula	C₄H₅N₃O₂
M_r	127.11
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	290
a, b, c (Å)	3.8823 (7), 17.499 (3), 8.8171 (17)
β (°)	100.938 (3)
V (Å³)	588.12 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.30 × 0.23 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.956, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	4285, 1098, 917
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.116, 1.06
No. of reflections	1098
No. of parameters	91
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.12

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1999) and CAMERON (Watkin et al., 1993), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···O1ⁱ	0.896 (19)	1.980 (19)	2.8659 (19)	169.56 (18)

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

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 Prof T. N. Guru Row, IISc, Bangalore, for useful crystallographic discussions. FNK thanks the DST for Fast Track Proposal funding.

References

Abu-Orabi, S. T., Alfah, M. A., Jibril, I., Mari'i, F. M. & Ali, A. A. S. (1989). J. Heterocycl. Chem. 26, 1461–1468. CrossRef CAS Google Scholar
Bruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dehne, H. (1994). Methoden der Organischen Chemie, Vol. E8d, edited by E. Schaumann, pp. 305–405. Stuttgart: Thieme. Google Scholar
Fan, W.-Q. & Katritzky, A. R. (1996). Comprehensive Heterocyclic Chemistry II, Vol. 4, edited by A. R. Katritzky, C. W. Rees & E. F. V Scriven, pp. 1–126. Oxford: Pergamon. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Z., Jian, F., Duan, C., Bai, Z. & You, X. (1998). Acta Cryst. C54, 1927–1929. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Watkin, D. J., Pearce, L. & Prout, C. K. (1993). CAMERON. Chemical Crystallography Laboratory, University of Oxford, England. Google Scholar