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

Hua, T.-J.; Sun, F.-M.; Liu, W.-J.; Qu, Y.-N.

doi:10.1107/S1600536808034430

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page o2351

doi:10.1107/S1600536808034430

Open

access

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

Tian-Jia Hua,^a Feng-Mei Sun,^b Wen-Ju Liu ^c ^* and Yong-Nian Qu ^a

^aDepartment of Medicinal Chemistry, Yunyang Medical College, Shiyan 442000, People's Republic of China, ^bSchool of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Xinxiang, 453003, People's Republic of China, and ^cDepartment of Chemistry and Life Science, Xianning College, Xianning 4371000, People's Republic of China
^*Correspondence e-mail: lwj_018@yahoo.com.cn

(Received 17 October 2008; accepted 21 October 2008; online 13 November 2008)

In the title compound, C₁₂H₁₃ClN₄O₂, the triazole ring carries methyl and ethoxycarbonyl groups, and is bound via a methylene bridge to a chloropyridine unit. There is evidence for significant electron delocalization in the triazolyl system. Intramolecular C—H⋯O and intermolecular C—H⋯N hydrogen bonds stabilize the structure.

Related literature

For applications of triazoles, see: Abu-Orabi et al. (1989 ); Fan & Katritzky (1996 ); Dehne (1994 ); Wang et al. (1998 ). For bond-length data, see: Sasada (1984 ).

Experimental

Crystal data

C₁₂H₁₃ClN₄O₂
M_r = 280.71
Monoclinic, P 2₁ /c
a = 24.984 (4) Å
b = 4.3919 (8) Å
c = 12.040 (2) Å
β = 94.415 (2)°
V = 1317.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 291 (2) K
0.46 × 0.38 × 0.33 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: none
9219 measured reflections
2450 independent reflections
1991 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.105
S = 1.05
2450 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.18 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
C5—H5⋯N3ⁱ	0.93	2.57	3.479 (3)	164
C9—H9A⋯N4ⁱⁱ	0.96	2.59	3.523 (3)	164
C9—H9B⋯O2	0.96	2.54	3.114 (3)	119
Symmetry codes: (i) $[x, -y+{\script{5\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808034430/at2655sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034430/at2655Isup2.hkl

checkCIF report

Comment top

[1,2,3]-Triazoles have been widely used in pharmaceuticals, agrochemicals, dyes, photographic materials, and in corrosion inhibition (Fan & Katritzky, 1996; Dehne,1994; Abu-Orabi et al., 1989). 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.

The C—N bonds are significantly shorter than a normal single C—N bond [1.47 Å; Sasada, 1984], and closer to the value for a C=N bond [1.28 Å; Wang et al., 1998]. This indicates significant electron delocalization in the triazolyl system.

Intramolecular C—H···O and intermolecular C—H···N hydrogen bonds contribute strongly to the stability of the molecular configuration (Table 1, Fig. 2).

Related literature top

For applications of triazoles, see: Abu-Orabi et al. (1989); Fan & Katritzky (1996); Dehne (1994); Wang et al. (1998). For bond-length data, see: Sasada (1984).

Experimental top

Ethyl acetylacetate (2 mmol) and 5-azidomethyl-2-chloropyridine (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 (2:1, v/v).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the molecular structure of (I), showing the atom labelling schemeand 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-bonds (dashed lines).

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

Crystal data top

C₁₂H₁₃ClN₄O₂	F(000) = 584
M_r = 280.71	D_x = 1.416 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3288 reflections
a = 24.984 (4) Å	θ = 3.3–25.5°
b = 4.3919 (8) Å	µ = 0.29 mm⁻¹
c = 12.040 (2) Å	T = 291 K
β = 94.415 (2)°	Block, colourless
V = 1317.2 (4) Å³	0.46 × 0.38 × 0.33 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1991 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 25.5°, θ_min = 3.3°
ϕ and ω scans	h = −30→29
9219 measured reflections	k = −5→5
2450 independent reflections	l = −14→14

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) = 0.105	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0461P)² + 0.4886P] where P = (F_o² + 2F_c²)/3
2450 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₂H₁₃ClN₄O₂	V = 1317.2 (4) Å³
M_r = 280.71	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 24.984 (4) Å	µ = 0.29 mm⁻¹
b = 4.3919 (8) Å	T = 291 K
c = 12.040 (2) Å	0.46 × 0.38 × 0.33 mm
β = 94.415 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1991 reflections with I > 2σ(I)
9219 measured reflections	R_int = 0.023
2450 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.05	Δρ_max = 0.19 e Å⁻³
2450 reflections	Δρ_min = −0.23 e Å⁻³
174 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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
Cl1	0.46436 (2)	0.66788 (16)	0.65329 (5)	0.0704 (2)
O1	0.11409 (5)	0.5500 (3)	0.20263 (11)	0.0531 (4)
O2	0.09737 (6)	0.7643 (4)	0.36514 (13)	0.0737 (5)
N1	0.37666 (7)	0.9857 (5)	0.61900 (13)	0.0649 (5)
N2	0.25163 (6)	1.1289 (3)	0.32725 (12)	0.0424 (4)
N3	0.25643 (6)	0.9861 (4)	0.22765 (12)	0.0489 (4)
N4	0.21318 (6)	0.8240 (4)	0.20603 (13)	0.0471 (4)
C1	0.41512 (7)	0.8561 (5)	0.56801 (16)	0.0484 (5)
C2	0.41911 (8)	0.8610 (6)	0.45476 (17)	0.0593 (6)
H2	0.4473	0.7647	0.4228	0.071*
C3	0.37992 (8)	1.0133 (6)	0.39049 (16)	0.0576 (6)
H3	0.3814	1.0215	0.3136	0.069*
C4	0.33851 (7)	1.1538 (4)	0.43968 (14)	0.0426 (4)
C5	0.33924 (9)	1.1340 (6)	0.55394 (16)	0.0625 (6)
H5	0.3118	1.2305	0.5885	0.075*
C6	0.29525 (8)	1.3267 (5)	0.37236 (17)	0.0507 (5)
H6A	0.2806	1.4811	0.4191	0.061*
H6B	0.3109	1.4293	0.3113	0.061*
C7	0.20468 (7)	1.0550 (4)	0.36960 (14)	0.0415 (4)
C8	0.18046 (7)	0.8611 (4)	0.29077 (14)	0.0413 (4)
C9	0.18798 (9)	1.1716 (5)	0.47790 (16)	0.0597 (6)
H9A	0.2023	1.0422	0.5372	0.090*
H9B	0.1495	1.1728	0.4764	0.090*
H9C	0.2013	1.3748	0.4899	0.090*
C10	0.12697 (8)	0.7226 (5)	0.29187 (16)	0.0477 (5)
C11	0.06017 (8)	0.4189 (6)	0.19684 (19)	0.0606 (6)
H11A	0.0336	0.5791	0.1999	0.073*
H11B	0.0567	0.2824	0.2592	0.073*
C12	0.05159 (10)	0.2481 (6)	0.0894 (2)	0.0700 (7)
H12A	0.0555	0.3845	0.0283	0.105*
H12B	0.0161	0.1623	0.0833	0.105*
H12C	0.0776	0.0878	0.0878	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0538 (3)	0.0928 (5)	0.0629 (4)	0.0083 (3)	−0.0057 (2)	0.0110 (3)
O1	0.0436 (7)	0.0630 (9)	0.0533 (8)	−0.0077 (6)	0.0074 (6)	−0.0061 (7)
O2	0.0623 (9)	0.1011 (13)	0.0607 (9)	−0.0154 (9)	0.0240 (8)	−0.0149 (9)
N1	0.0567 (10)	0.1005 (15)	0.0377 (9)	0.0146 (10)	0.0050 (8)	−0.0002 (10)
N2	0.0477 (8)	0.0423 (8)	0.0367 (8)	0.0002 (7)	0.0010 (6)	0.0047 (7)
N3	0.0515 (9)	0.0565 (10)	0.0392 (8)	−0.0032 (8)	0.0071 (7)	−0.0004 (7)
N4	0.0486 (9)	0.0538 (10)	0.0391 (8)	−0.0028 (8)	0.0047 (7)	−0.0002 (7)
C1	0.0432 (10)	0.0573 (12)	0.0444 (10)	−0.0048 (9)	0.0015 (8)	0.0010 (9)
C2	0.0496 (11)	0.0821 (16)	0.0476 (11)	0.0122 (11)	0.0130 (9)	−0.0023 (11)
C3	0.0568 (12)	0.0809 (16)	0.0362 (10)	0.0054 (11)	0.0110 (9)	0.0024 (10)
C4	0.0457 (10)	0.0429 (10)	0.0392 (10)	−0.0068 (8)	0.0029 (7)	−0.0024 (8)
C5	0.0570 (12)	0.0909 (17)	0.0404 (11)	0.0193 (12)	0.0078 (9)	−0.0083 (11)
C6	0.0559 (11)	0.0436 (11)	0.0515 (11)	−0.0048 (9)	−0.0017 (9)	0.0015 (9)
C7	0.0480 (10)	0.0422 (10)	0.0342 (9)	0.0067 (8)	0.0022 (7)	0.0066 (8)
C8	0.0448 (10)	0.0443 (10)	0.0349 (9)	0.0038 (8)	0.0034 (7)	0.0052 (8)
C9	0.0690 (13)	0.0692 (15)	0.0416 (11)	0.0010 (12)	0.0092 (9)	−0.0065 (10)
C10	0.0468 (10)	0.0517 (11)	0.0447 (10)	0.0020 (9)	0.0050 (8)	0.0046 (9)
C11	0.0448 (11)	0.0683 (14)	0.0692 (14)	−0.0100 (10)	0.0085 (10)	−0.0011 (11)
C12	0.0587 (13)	0.0816 (17)	0.0690 (15)	−0.0187 (12)	0.0004 (11)	−0.0038 (13)

Geometric parameters (Å, º) top

Cl1—C1	1.748 (2)	C4—C6	1.505 (3)
O1—C10	1.334 (2)	C5—H5	0.9300
O1—C11	1.462 (2)	C6—H6A	0.9700
O2—C10	1.208 (2)	C6—H6B	0.9700
N1—C1	1.310 (3)	C7—C8	1.380 (3)
N1—C5	1.341 (3)	C7—C9	1.490 (3)
N2—C7	1.354 (2)	C8—C10	1.469 (3)
N2—N3	1.367 (2)	C9—H9A	0.9600
N2—C6	1.465 (2)	C9—H9B	0.9600
N3—N4	1.303 (2)	C9—H9C	0.9600
N4—C8	1.365 (2)	C11—C12	1.496 (3)
C1—C2	1.375 (3)	C11—H11A	0.9700
C2—C3	1.374 (3)	C11—H11B	0.9700
C2—H2	0.9300	C12—H12A	0.9600
C3—C4	1.377 (3)	C12—H12B	0.9600
C3—H3	0.9300	C12—H12C	0.9600
C4—C5	1.377 (3)

C10—O1—C11	115.24 (15)	N2—C7—C8	103.62 (15)
C1—N1—C5	116.16 (17)	N2—C7—C9	123.82 (17)
C7—N2—N3	110.96 (15)	C8—C7—C9	132.56 (18)
C7—N2—C6	130.06 (16)	N4—C8—C7	109.36 (16)
N3—N2—C6	118.97 (15)	N4—C8—C10	123.69 (16)
N4—N3—N2	107.36 (14)	C7—C8—C10	126.89 (16)
N3—N4—C8	108.69 (15)	C7—C9—H9A	109.5
N1—C1—C2	124.75 (19)	C7—C9—H9B	109.5
N1—C1—Cl1	116.01 (15)	H9A—C9—H9B	109.5
C2—C1—Cl1	119.23 (16)	C7—C9—H9C	109.5
C3—C2—C1	117.59 (18)	H9A—C9—H9C	109.5
C3—C2—H2	121.2	H9B—C9—H9C	109.5
C1—C2—H2	121.2	O2—C10—O1	123.45 (18)
C2—C3—C4	120.15 (18)	O2—C10—C8	123.52 (19)
C2—C3—H3	119.9	O1—C10—C8	113.02 (16)
C4—C3—H3	119.9	O1—C11—C12	107.99 (17)
C5—C4—C3	116.66 (18)	O1—C11—H11A	110.1
C5—C4—C6	121.56 (17)	C12—C11—H11A	110.1
C3—C4—C6	121.77 (17)	O1—C11—H11B	110.1
N1—C5—C4	124.68 (19)	C12—C11—H11B	110.1
N1—C5—H5	117.7	H11A—C11—H11B	108.4
C4—C5—H5	117.7	C11—C12—H12A	109.5
N2—C6—C4	112.53 (15)	C11—C12—H12B	109.5
N2—C6—H6A	109.1	H12A—C12—H12B	109.5
C4—C6—H6A	109.1	C11—C12—H12C	109.5
N2—C6—H6B	109.1	H12A—C12—H12C	109.5
C4—C6—H6B	109.1	H12B—C12—H12C	109.5
H6A—C6—H6B	107.8

C7—N2—N3—N4	0.3 (2)	N3—N2—C7—C8	−0.43 (19)
C6—N2—N3—N4	179.64 (15)	C6—N2—C7—C8	−179.72 (17)
N2—N3—N4—C8	0.0 (2)	N3—N2—C7—C9	179.32 (17)
C5—N1—C1—C2	−0.5 (3)	C6—N2—C7—C9	0.0 (3)
C5—N1—C1—Cl1	179.07 (18)	N3—N4—C8—C7	−0.3 (2)
N1—C1—C2—C3	0.1 (4)	N3—N4—C8—C10	177.11 (17)
Cl1—C1—C2—C3	−179.46 (17)	N2—C7—C8—N4	0.5 (2)
C1—C2—C3—C4	−0.1 (3)	C9—C7—C8—N4	−179.3 (2)
C2—C3—C4—C5	0.5 (3)	N2—C7—C8—C10	−176.87 (17)
C2—C3—C4—C6	179.1 (2)	C9—C7—C8—C10	3.4 (3)
C1—N1—C5—C4	1.0 (4)	C11—O1—C10—O2	1.9 (3)
C3—C4—C5—N1	−1.0 (4)	C11—O1—C10—C8	−177.09 (17)
C6—C4—C5—N1	−179.6 (2)	N4—C8—C10—O2	−177.4 (2)
C7—N2—C6—C4	93.0 (2)	C7—C8—C10—O2	−0.4 (3)
N3—N2—C6—C4	−86.3 (2)	N4—C8—C10—O1	1.6 (3)
C5—C4—C6—N2	−96.2 (2)	C7—C8—C10—O1	178.57 (17)
C3—C4—C6—N2	85.3 (2)	C10—O1—C11—C12	176.97 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N3ⁱ	0.93	2.57	3.479 (3)	164
C9—H9A···N4ⁱⁱ	0.96	2.59	3.523 (3)	164
C9—H9B···O2	0.96	2.54	3.114 (3)	119

Symmetry codes: (i) x, −y+5/2, z+1/2; (ii) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃ClN₄O₂
M_r	280.71
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	291
a, b, c (Å)	24.984 (4), 4.3919 (8), 12.040 (2)
β (°)	94.415 (2)
V (Å³)	1317.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.46 × 0.38 × 0.33

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9219, 2450, 1991
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.105, 1.05
No. of reflections	2450
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.23

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···N3ⁱ	0.93	2.57	3.479 (3)	164
C9—H9A···N4ⁱⁱ	0.96	2.59	3.523 (3)	164
C9—H9B···O2	0.96	2.54	3.114 (3)	119

Symmetry codes: (i) x, −y+5/2, z+1/2; (ii) x, −y+3/2, z+1/2.

Acknowledgements

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

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 (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dehne, H. (1994). In Methoden der Organischen Chemie (Houben-Weyl), Vol. E8d, edited by E. Schumann, pp. 305–405. Stuttgart: Thieme. Google Scholar
Fan, W.-Q. & Katritzky, A. R. (1996). In 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
Sasada, Y. (1984). Molecular and Crystal Structures. In Chemistry Handbook, 3rd ed. Tokyo: The Chemical Society of Japan, Maruzen. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. 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