Methyl 1-(2,6-difluoro­benz­yl)-1H-1,2,3-triazole-4-carboxyl­ate

Dong, S.-L.; Cheng, X.-C.

doi:10.1107/S1600536811006684

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o769

doi:10.1107/S1600536811006684

Open

access

Methyl 1-(2,6-difluorobenzyl)-1H-1,2,3-triazole-4-carboxylate

Su-Lan Dong ^a ^* and Xiao-Chun Cheng ^a

^aCollege of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaiyin 223003, Jiangsu, People's Republic of China
^*Correspondence e-mail: dsl710221@163.com

(Received 11 January 2011; accepted 22 February 2011; online 2 March 2011)

In the title compound, C₁₁H₉F₂N₃O₂, the triazole ring is planar, with an r.m.s. deviation of 0.0048 Å, and makes a dihedral angle of 77.3 (1)° with the benzene ring. In the crystal, weak intermolecular C—H⋯O and C—H⋯N hydrogen bonds link the molecules into chains along the b axis.

Related literature

For the synthetic procedure and applications of the title compound, see: Arroyo (2007 ). The title compound is an intermediate in the preparation of the anticonvulsant drug rufinamide [systematic name 1-(2,6-difluorobenzyl)-1H-1,2,3-triazole-4-carboxamide], see: Meier (1986 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₉F₂N₃O₂
M_r = 253.21
Monoclinic, P 2₁
a = 8.4570 (17) Å
b = 5.4140 (11) Å
c = 12.125 (2) Å
β = 92.28 (3)°
V = 554.72 (18) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.962, T_max = 0.987
2187 measured reflections
1146 independent reflections
1035 reflections with I > 2σ(I)
R_int = 0.031
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.088
S = 1.04
1146 reflections
164 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.13 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
C7—H7B⋯N3ⁱ	0.97	2.62	3.538 (4)	157
C8—H8A⋯O1ⁱⁱ	0.93	2.35	3.243 (3)	162
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); 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 I, global. DOI: 10.1107/S1600536811006684/bq2275sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811006684/bq2275Isup2.hkl

checkCIF report

Comment top

The title compound C₁₁H₉F₂N₃O₂, (I), was synthesized by the reaction of 2,6-fluorobenzyl azide and methyl propiolate (Arroyo, 2007), and it is an important organic intermediate which is useful in preparing medicine rufinamide (Meier, 1986).

The molecular structure of (I) is shown in Fig. 1, the bond lengths and angles are within normal ranges (Allen et al., 1987). For synthetic procedure, see: Meier, 1986. For background to the applications, see: Arroyo, 2007.

Ring A (C1—C6) and B (C8/C9/N1/N2/N3) are planar with r.m.s. deviations of 0.0048 ° and 0.0022 °, respectively, and the dihedral angle between them is 77.3 (1) ° (Fig.1).

As can be seen from the packing diagram (Fig.2), the crystal packing is stabilized by intermolecular C—H···O and C—H···N hydrogen bonds along the b axis.

Related literature top

For the synthetic procedure and applications of the title compound, see: Arroyo (2007). The title compound is an intermediate in the preparation of the anticonvulsant drug rufinamide [systematic name 1-(2,6-difluorobenzyl)-1H-1,2,3-triazole-4-carboxamide], see: Meier (1986). For bond-length data, see: Allen et al. (1987).

Experimental top

A mixture of 2,6-fluorobenzyl azide (390 g, 1.66 mol), methyl propiolate (165 g, 1.97 mol) and methanol (2 L) was stirred and refluxed for 10 h. Removing of the solvent under reduced pressure gave a yellowish soil. The soil could be recrystallized using a mixture of petroleum ether and methanol (4:1) and product to be a white and spiculate soil (yield; 299 g, 51.8%, m.p. 413 K). Crystals of (I) suitable for x-ray diffraction were obtained by slow evaporation from methylalcohol (AR) (10 ml).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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 title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal structure of (I). Dashed lines indicate C—H···N and the C—H···O hydrogen bonds.

Methyl 1-(2,6-difluorobenzyl)-1H-1,2,3-triazole-4-carboxylate top

Crystal data top

C₁₁H₉F₂N₃O₂	F(000) = 260
M_r = 253.21	D_x = 1.516 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 8.4570 (17) Å	θ = 10–14°
b = 5.4140 (11) Å	µ = 0.13 mm⁻¹
c = 12.125 (2) Å	T = 298 K
β = 92.28 (3)°	Spiculate, colorless
V = 554.72 (18) Å³	0.30 × 0.20 × 0.10 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	1035 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 25.4°, θ_min = 1.7°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −6→6
T_min = 0.962, T_max = 0.987	l = −14→14
2187 measured reflections	3 standard reflections every 200 reflections
1146 independent reflections	intensity decay: 1%

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.088	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0542P)² + 0.0317P] where P = (F_o² + 2F_c²)/3
1146 reflections	(Δ/σ)_max < 0.001
164 parameters	Δρ_max = 0.13 e Å⁻³
1 restraint	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₁H₉F₂N₃O₂	V = 554.72 (18) Å³
M_r = 253.21	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.4570 (17) Å	µ = 0.13 mm⁻¹
b = 5.4140 (11) Å	T = 298 K
c = 12.125 (2) Å	0.30 × 0.20 × 0.10 mm
β = 92.28 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1035 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.031
T_min = 0.962, T_max = 0.987	3 standard reflections every 200 reflections
2187 measured reflections	intensity decay: 1%
1146 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	1 restraint
wR(F²) = 0.088	H-atom parameters constrained
S = 1.04	Δρ_max = 0.13 e Å⁻³
1146 reflections	Δρ_min = −0.17 e Å⁻³
164 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
N1	0.4481 (2)	0.4288 (4)	0.80667 (14)	0.0340 (5)
F1	0.67849 (18)	0.9724 (4)	0.74993 (14)	0.0589 (5)
O1	0.3504 (3)	0.2067 (5)	0.47974 (15)	0.0642 (6)
C1	0.7743 (3)	0.7947 (5)	0.7942 (2)	0.0409 (6)
F2	0.74809 (18)	0.2564 (4)	0.96110 (13)	0.0595 (5)
N2	0.3697 (2)	0.2386 (5)	0.85061 (16)	0.0424 (5)
O2	0.2160 (2)	−0.0844 (5)	0.56720 (16)	0.0613 (6)
C2	0.9334 (3)	0.8063 (6)	0.7754 (2)	0.0500 (7)
H2B	0.9745	0.9332	0.7336	0.060*
N3	0.3078 (2)	0.1088 (5)	0.76968 (17)	0.0436 (5)
C3	1.0299 (3)	0.6249 (7)	0.8204 (2)	0.0527 (7)
H3B	1.1377	0.6284	0.8080	0.063*
C4	0.9699 (3)	0.4388 (7)	0.8831 (2)	0.0517 (7)
H4A	1.0354	0.3168	0.9137	0.062*
C5	0.8097 (3)	0.4382 (5)	0.89946 (19)	0.0409 (6)
C6	0.7066 (3)	0.6141 (5)	0.85681 (19)	0.0361 (5)
C7	0.5322 (3)	0.6069 (5)	0.87801 (19)	0.0373 (6)
H7A	0.5179	0.5633	0.9546	0.045*
H7B	0.4873	0.7699	0.8655	0.045*
C8	0.4362 (3)	0.4207 (6)	0.69632 (18)	0.0374 (5)
H8A	0.4792	0.5303	0.6466	0.045*
C9	0.3472 (3)	0.2167 (5)	0.67313 (19)	0.0368 (6)
C10	0.3059 (3)	0.1160 (6)	0.5631 (2)	0.0438 (6)
C11	0.1788 (5)	−0.2037 (8)	0.4633 (3)	0.0797 (11)
H11A	0.1137	−0.3457	0.4753	0.120*
H11B	0.2749	−0.2545	0.4304	0.120*
H11C	0.1229	−0.0904	0.4149	0.120*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0291 (9)	0.0382 (11)	0.0349 (9)	0.0038 (10)	0.0041 (7)	0.0054 (10)
F1	0.0558 (9)	0.0504 (10)	0.0709 (10)	0.0116 (9)	0.0070 (8)	0.0213 (9)
O1	0.0899 (15)	0.0602 (15)	0.0430 (10)	−0.0071 (15)	0.0099 (10)	−0.0047 (11)
C1	0.0411 (13)	0.0375 (15)	0.0441 (13)	0.0042 (12)	0.0002 (10)	−0.0002 (12)
F2	0.0514 (9)	0.0533 (11)	0.0742 (11)	0.0048 (9)	0.0064 (8)	0.0239 (10)
N2	0.0395 (10)	0.0474 (14)	0.0406 (11)	−0.0038 (11)	0.0050 (9)	0.0102 (11)
O2	0.0674 (12)	0.0578 (14)	0.0587 (11)	−0.0161 (13)	0.0018 (10)	−0.0111 (12)
C2	0.0450 (14)	0.0477 (17)	0.0580 (15)	−0.0094 (14)	0.0106 (12)	−0.0005 (15)
N3	0.0398 (11)	0.0470 (13)	0.0442 (11)	−0.0052 (11)	0.0038 (9)	0.0076 (11)
C3	0.0364 (13)	0.0589 (19)	0.0630 (17)	−0.0032 (15)	0.0059 (12)	−0.0071 (16)
C4	0.0367 (13)	0.0536 (18)	0.0644 (16)	0.0064 (15)	−0.0027 (12)	−0.0005 (17)
C5	0.0380 (12)	0.0394 (15)	0.0451 (12)	0.0027 (13)	0.0018 (10)	0.0046 (13)
C6	0.0335 (11)	0.0396 (13)	0.0353 (11)	0.0012 (12)	0.0013 (9)	−0.0037 (11)
C7	0.0361 (11)	0.0383 (14)	0.0377 (11)	0.0041 (12)	0.0033 (9)	−0.0012 (11)
C8	0.0381 (11)	0.0386 (13)	0.0361 (11)	0.0020 (12)	0.0076 (9)	0.0045 (12)
C9	0.0316 (10)	0.0386 (14)	0.0403 (12)	0.0033 (11)	0.0042 (9)	0.0014 (12)
C10	0.0438 (13)	0.0389 (14)	0.0489 (15)	0.0073 (13)	0.0051 (11)	−0.0037 (13)
C11	0.098 (3)	0.068 (3)	0.073 (2)	−0.016 (2)	−0.0032 (19)	−0.025 (2)

Geometric parameters (Å, º) top

N1—C8	1.339 (3)	C3—C4	1.372 (4)
N1—N2	1.346 (3)	C3—H3B	0.9300
N1—C7	1.461 (3)	C4—C5	1.377 (3)
F1—C1	1.355 (3)	C4—H4A	0.9300
O1—C10	1.198 (3)	C5—C6	1.378 (4)
C1—C2	1.375 (4)	C6—C7	1.507 (3)
C1—C6	1.376 (4)	C7—H7A	0.9700
F2—C5	1.353 (3)	C7—H7B	0.9700
N2—N3	1.300 (3)	C8—C9	1.360 (4)
O2—C10	1.327 (4)	C8—H8A	0.9300
O2—C11	1.439 (4)	C9—C10	1.471 (4)
C2—C3	1.376 (5)	C11—H11A	0.9600
C2—H2B	0.9300	C11—H11B	0.9600
N3—C9	1.362 (3)	C11—H11C	0.9600

C8—N1—N2	110.6 (2)	C1—C6—C7	122.9 (2)
C8—N1—C7	129.0 (2)	N1—C7—C6	111.9 (2)
N2—N1—C7	120.43 (18)	N1—C7—H7A	109.2
F1—C1—C2	118.4 (3)	C6—C7—H7A	109.2
F1—C1—C6	117.9 (2)	N1—C7—H7B	109.2
C2—C1—C6	123.7 (3)	C6—C7—H7B	109.2
N3—N2—N1	107.75 (18)	H7A—C7—H7B	107.9
C10—O2—C11	116.1 (3)	N1—C8—C9	104.6 (2)
C1—C2—C3	118.1 (3)	N1—C8—H8A	127.7
C1—C2—H2B	120.9	C9—C8—H8A	127.7
C3—C2—H2B	120.9	C8—C9—N3	108.9 (2)
N2—N3—C9	108.2 (2)	C8—C9—C10	126.8 (2)
C4—C3—C2	121.1 (2)	N3—C9—C10	124.3 (2)
C4—C3—H3B	119.4	O1—C10—O2	124.5 (3)
C2—C3—H3B	119.4	O1—C10—C9	122.8 (3)
C3—C4—C5	118.0 (3)	O2—C10—C9	112.7 (2)
C3—C4—H4A	121.0	O2—C11—H11A	109.5
C5—C4—H4A	121.0	O2—C11—H11B	109.5
F2—C5—C6	117.3 (2)	H11A—C11—H11B	109.5
F2—C5—C4	118.9 (2)	O2—C11—H11C	109.5
C6—C5—C4	123.8 (3)	H11A—C11—H11C	109.5
C5—C6—C1	115.3 (2)	H11B—C11—H11C	109.5
C5—C6—C7	121.8 (2)

C8—N1—N2—N3	0.0 (3)	C8—N1—C7—C6	−59.3 (3)
C7—N1—N2—N3	−179.3 (2)	N2—N1—C7—C6	119.9 (2)
F1—C1—C2—C3	−179.8 (2)	C5—C6—C7—N1	−79.4 (3)
C6—C1—C2—C3	1.1 (4)	C1—C6—C7—N1	100.6 (3)
N1—N2—N3—C9	0.1 (3)	N2—N1—C8—C9	−0.2 (3)
C1—C2—C3—C4	−0.7 (5)	C7—N1—C8—C9	179.1 (2)
C2—C3—C4—C5	0.3 (4)	N1—C8—C9—N3	0.2 (3)
C3—C4—C5—F2	180.0 (2)	N1—C8—C9—C10	−176.5 (2)
C3—C4—C5—C6	−0.3 (4)	N2—N3—C9—C8	−0.2 (3)
F2—C5—C6—C1	−179.7 (2)	N2—N3—C9—C10	176.6 (2)
C4—C5—C6—C1	0.6 (4)	C11—O2—C10—O1	3.4 (4)
F2—C5—C6—C7	0.4 (4)	C11—O2—C10—C9	−176.1 (3)
C4—C5—C6—C7	−179.3 (3)	C8—C9—C10—O1	1.0 (4)
F1—C1—C6—C5	179.9 (2)	N3—C9—C10—O1	−175.3 (3)
C2—C1—C6—C5	−1.0 (4)	C8—C9—C10—O2	−179.4 (2)
F1—C1—C6—C7	−0.2 (4)	N3—C9—C10—O2	4.3 (3)
C2—C1—C6—C7	178.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···N3ⁱ	0.97	2.62	3.538 (4)	157
C8—H8A···O1ⁱⁱ	0.93	2.35	3.243 (3)	162

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

Experimental details

Crystal data
Chemical formula	C₁₁H₉F₂N₃O₂
M_r	253.21
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	8.4570 (17), 5.4140 (11), 12.125 (2)
β (°)	92.28 (3)
V (Å³)	554.72 (18)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.962, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	2187, 1146, 1035
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.088, 1.04
No. of reflections	1146
No. of parameters	164
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.17

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), 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
C7—H7B···N3ⁱ	0.97	2.62	3.538 (4)	157
C8—H8A···O1ⁱⁱ	0.93	2.35	3.243 (3)	162

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support. They also acknowledge the contract grant sponsors: the Natural Science Foundation of Jiangsu Province of China (BK2008195) and the Science Research Foundation of Huaiyin Institute of Technology (2517045).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Arroyo, S. (2007). Neurotherapeutics, A4, 155–162. CrossRef Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Meier, R. (1986). Eur. Patent No. 0199262. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar