Ethyl 2-(2-amino-5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7-yl)acetate

Gueddar, H.; Bouhfid, R.; Guessous, A.R.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536811054468

organic compounds

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Volume 68| Part 1| January 2012| Page o239

doi:10.1107/S1600536811054468

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Ethyl 2-(2-amino-5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7-yl)acetate

Hicham Gueddar,^a Rachid Bouhfid,^b Ahmed Radouane Guessous,^a El Mokhtar Essassi ^a and Seik Weng Ng ^c,^d ^*

^aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, ^bInstitute of Nanomaterials and Nanotechnology, MAScIR, Avenue de l'Armée Royale, Rabat, Morocco, ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^dChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 17 December 2011; accepted 18 December 2011; online 23 December 2011)

The nine-membered fused-ring of the title compound, C₁₀H₁₃N₅O₂, is approximately planar [maximum deviation = 0.012 (1) Å]; the bond angle at the methylene C atom is 111.33 (10)°. In the crystal, the amino group forms hydrogen bonds to the N atoms of the triazole rings of adjacent molecules, generating a ribbon running along the a axis.

Related literature

For a related molecule, see: Fettouhi et al. (1996 ).

Experimental

Crystal data

C₁₀H₁₃N₅O₂
M_r = 235.25
Monoclinic, C 2/c
a = 22.9635 (4) Å
b = 7.7447 (1) Å
c = 14.7017 (3) Å
β = 124.574 (1)°
V = 2152.87 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.32 × 0.21 × 0.20 mm

Data collection

Bruker APEX DUO diffractometer
21320 measured reflections
4613 independent reflections
3058 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.138
S = 1.02
4613 reflections
163 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H1⋯N2ⁱ	0.88 (1)	2.24 (1)	3.095 (1)	166 (2)
N5—H2⋯N3ⁱⁱ	0.89 (1)	2.15 (1)	3.037 (2)	175 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811054468/xu5412sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811054468/xu5412Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811054468/xu5412Isup3.cml

checkCIF report

Comment top

We reported the reaction of 3-diamino-1,2,4-triazole and 4-hydroxy-6-methyl-pyran-2-one to form ethyl 2-(2-amino-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-yl)acetate (Fettouhi et al., 1996), which is a member of a class of antiviral compounds. The use of 3,5-diamino-1,2,4-triazol with the pyrone gave the analogous amino-substituted compound (Scheme I). The nine-membered fused-ring of C₁₀H₁₃N₅O₂ is planar; the methylene unit connecting the fused-ring and the ethoxycarbonyl unit is slightly opened up to 111.33 (10)° (Fig. 1). The amino group forms hydrogen bonds to the N atoms of the triazole rings of adjacent molecules by a two-fold symmetry operation to generate a ribbon running along the a-axis of the monoclinic unit cell (Table 1).

Related literature top

For a related molecule, see: Fettouhi et al. (1996).

Experimental top

A solution of 3,5-diamino-1,2,4-triazole (1 g, 10 mmol) and 4-hydroxy-6-methyl-pyran-2-one (1.6g, 12.6 mmol) in ethanol (30 ml) was heated for 12 hours. The solvent was removed by evaporation and the residue recrystallized from ethanol to afford the colorless crystals.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₀H₁₃N₅O₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Ethyl 2-(2-amino-5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7-yl)acetate top

Crystal data top

C₁₀H₁₃N₅O₂	F(000) = 992
M_r = 235.25	D_x = 1.452 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3608 reflections
a = 22.9635 (4) Å	θ = 2.8–35.5°
b = 7.7447 (1) Å	µ = 0.11 mm⁻¹
c = 14.7017 (3) Å	T = 293 K
β = 124.574 (1)°	Prism, colorless
V = 2152.87 (6) Å³	0.32 × 0.21 × 0.20 mm
Z = 8

Data collection top

Bruker APEX DUO diffractometer	3058 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 34.7°, θ_min = 2.8°
ω scans	h = −35→36
21320 measured reflections	k = −12→9
4613 independent reflections	l = −23→22

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0666P)² + 0.6364P] where P = (F_o² + 2F_c²)/3
4613 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.50 e Å⁻³
2 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₀H₁₃N₅O₂	V = 2152.87 (6) Å³
M_r = 235.25	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 22.9635 (4) Å	µ = 0.11 mm⁻¹
b = 7.7447 (1) Å	T = 293 K
c = 14.7017 (3) Å	0.32 × 0.21 × 0.20 mm
β = 124.574 (1)°

Data collection top

Bruker APEX DUO diffractometer	3058 reflections with I > 2σ(I)
21320 measured reflections	R_int = 0.050
4613 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	2 restraints
wR(F²) = 0.138	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.50 e Å⁻³
4613 reflections	Δρ_min = −0.32 e Å⁻³
163 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.66634 (4)	0.58516 (12)	0.48590 (7)	0.01669 (18)
O2	0.59517 (5)	0.70201 (15)	0.31780 (7)	0.0279 (2)
N1	0.60826 (5)	0.99885 (13)	0.53229 (7)	0.01076 (18)
N2	0.67164 (5)	0.93485 (13)	0.61966 (7)	0.01190 (18)
N3	0.66734 (5)	1.23064 (13)	0.63055 (8)	0.01260 (19)
N4	0.55068 (5)	1.27125 (14)	0.46404 (8)	0.01363 (19)
N5	0.77145 (5)	1.08068 (14)	0.76545 (8)	0.0147 (2)
C1	0.77877 (6)	0.45604 (19)	0.56140 (11)	0.0200 (3)
H1A	0.8124	0.4183	0.5466	0.030*
H1B	0.7646	0.3596	0.5856	0.030*
H1C	0.8000	0.5427	0.6181	0.030*
C2	0.71486 (6)	0.53072 (18)	0.45759 (10)	0.0177 (2)
H2A	0.7284	0.6284	0.4321	0.021*
H2B	0.6928	0.4445	0.3995	0.021*
C3	0.60866 (6)	0.66849 (16)	0.40788 (9)	0.0151 (2)
C4	0.56130 (6)	0.71606 (16)	0.44533 (9)	0.0140 (2)
H4A	0.5150	0.6649	0.3955	0.017*
H4B	0.5811	0.6694	0.5186	0.017*
C5	0.55386 (5)	0.90755 (15)	0.44764 (9)	0.0118 (2)
C6	0.49644 (6)	1.00289 (16)	0.36969 (9)	0.0133 (2)
H6	0.4573	0.9479	0.3099	0.016*
C7	0.49650 (6)	1.18385 (16)	0.37998 (9)	0.0135 (2)
C8	0.43393 (6)	1.28736 (18)	0.29316 (10)	0.0188 (2)
H8A	0.4375	1.4029	0.3195	0.028*
H8B	0.3912	1.2349	0.2773	0.028*
H8C	0.4331	1.2904	0.2271	0.028*
C9	0.60642 (6)	1.17669 (15)	0.54011 (9)	0.0114 (2)
C10	0.70439 (6)	1.08132 (15)	0.67461 (9)	0.0115 (2)
H1	0.7866 (9)	1.1735 (16)	0.8069 (12)	0.027 (4)*
H2	0.7920 (8)	0.9812 (15)	0.7978 (13)	0.027 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0130 (4)	0.0209 (5)	0.0142 (4)	0.0049 (3)	0.0066 (3)	0.0026 (3)
O2	0.0328 (5)	0.0336 (6)	0.0165 (4)	0.0168 (5)	0.0135 (4)	0.0082 (4)
N1	0.0087 (4)	0.0096 (4)	0.0101 (4)	0.0000 (3)	0.0030 (3)	−0.0006 (3)
N2	0.0087 (4)	0.0104 (5)	0.0101 (4)	0.0000 (3)	0.0015 (3)	0.0003 (3)
N3	0.0108 (4)	0.0102 (4)	0.0118 (4)	−0.0001 (3)	0.0034 (3)	−0.0002 (3)
N4	0.0108 (4)	0.0114 (5)	0.0145 (4)	0.0010 (3)	0.0047 (3)	0.0007 (4)
N5	0.0122 (4)	0.0110 (5)	0.0113 (4)	−0.0002 (4)	0.0009 (3)	−0.0004 (4)
C1	0.0147 (5)	0.0207 (6)	0.0225 (6)	0.0038 (4)	0.0094 (4)	0.0025 (5)
C2	0.0178 (5)	0.0181 (6)	0.0180 (5)	0.0034 (5)	0.0106 (4)	−0.0006 (5)
C3	0.0148 (5)	0.0116 (5)	0.0138 (5)	0.0009 (4)	0.0050 (4)	−0.0017 (4)
C4	0.0118 (4)	0.0102 (5)	0.0153 (5)	−0.0013 (4)	0.0049 (4)	−0.0020 (4)
C5	0.0093 (4)	0.0116 (5)	0.0116 (4)	−0.0015 (4)	0.0043 (4)	−0.0025 (4)
C6	0.0091 (4)	0.0140 (5)	0.0115 (4)	−0.0001 (4)	0.0028 (4)	−0.0016 (4)
C7	0.0100 (4)	0.0147 (6)	0.0125 (4)	0.0007 (4)	0.0044 (4)	0.0003 (4)
C8	0.0122 (5)	0.0170 (6)	0.0178 (5)	0.0039 (4)	0.0028 (4)	0.0027 (5)
C9	0.0113 (4)	0.0087 (5)	0.0124 (4)	0.0004 (4)	0.0057 (4)	0.0000 (4)
C10	0.0112 (4)	0.0107 (5)	0.0104 (4)	−0.0007 (4)	0.0048 (4)	0.0001 (4)

Geometric parameters (Å, º) top

O1—C3	1.3276 (14)	C1—H1B	0.9600
O1—C2	1.4555 (15)	C1—H1C	0.9600
O2—C3	1.2049 (15)	C2—H2A	0.9700
N1—C5	1.3582 (14)	C2—H2B	0.9700
N1—N2	1.3755 (12)	C3—C4	1.5169 (17)
N1—C9	1.3847 (15)	C4—C5	1.4954 (17)
N2—C10	1.3474 (15)	C4—H4A	0.9700
N3—C9	1.3374 (14)	C4—H4B	0.9700
N3—C10	1.3621 (15)	C5—C6	1.3720 (15)
N4—C7	1.3373 (14)	C6—C7	1.4096 (17)
N4—C9	1.3419 (14)	C6—H6	0.9300
N5—C10	1.3494 (14)	C7—C8	1.5016 (16)
N5—H1	0.877 (9)	C8—H8A	0.9600
N5—H2	0.887 (9)	C8—H8B	0.9600
C1—C2	1.5085 (17)	C8—H8C	0.9600
C1—H1A	0.9600

C3—O1—C2	116.37 (9)	C5—C4—H4A	109.4
C5—N1—N2	127.13 (10)	C3—C4—H4A	109.4
C5—N1—C9	122.57 (9)	C5—C4—H4B	109.4
N2—N1—C9	110.30 (9)	C3—C4—H4B	109.4
C10—N2—N1	101.03 (9)	H4A—C4—H4B	108.0
C9—N3—C10	103.08 (10)	N1—C5—C6	115.69 (11)
C7—N4—C9	116.18 (10)	N1—C5—C4	118.66 (9)
C10—N5—H1	117.7 (11)	C6—C5—C4	125.64 (10)
C10—N5—H2	119.6 (11)	C5—C6—C7	120.23 (10)
H1—N5—H2	117.3 (15)	C5—C6—H6	119.9
C2—C1—H1A	109.5	C7—C6—H6	119.9
C2—C1—H1B	109.5	N4—C7—C6	123.11 (10)
H1A—C1—H1B	109.5	N4—C7—C8	117.06 (11)
C2—C1—H1C	109.5	C6—C7—C8	119.83 (10)
H1A—C1—H1C	109.5	C7—C8—H8A	109.5
H1B—C1—H1C	109.5	C7—C8—H8B	109.5
O1—C2—C1	106.55 (10)	H8A—C8—H8B	109.5
O1—C2—H2A	110.4	C7—C8—H8C	109.5
C1—C2—H2A	110.4	H8A—C8—H8C	109.5
O1—C2—H2B	110.4	H8B—C8—H8C	109.5
C1—C2—H2B	110.4	N3—C9—N4	128.53 (11)
H2A—C2—H2B	108.6	N3—C9—N1	109.22 (9)
O2—C3—O1	124.23 (11)	N4—C9—N1	122.23 (10)
O2—C3—C4	123.83 (11)	N2—C10—N5	121.70 (10)
O1—C3—C4	111.95 (10)	N2—C10—N3	116.37 (9)
C5—C4—C3	111.33 (10)	N5—C10—N3	121.86 (10)

C5—N1—N2—C10	178.81 (11)	C9—N4—C7—C8	−179.26 (11)
C9—N1—N2—C10	−0.44 (12)	C5—C6—C7—N4	−0.35 (18)
C3—O1—C2—C1	174.51 (11)	C5—C6—C7—C8	178.90 (11)
C2—O1—C3—O2	−0.81 (19)	C10—N3—C9—N4	−178.56 (12)
C2—O1—C3—C4	178.92 (10)	C10—N3—C9—N1	0.13 (12)
O2—C3—C4—C5	−62.89 (16)	C7—N4—C9—N3	178.85 (11)
O1—C3—C4—C5	117.38 (11)	C7—N4—C9—N1	0.31 (16)
N2—N1—C5—C6	−179.22 (10)	C5—N1—C9—N3	−179.09 (10)
C9—N1—C5—C6	−0.05 (16)	N2—N1—C9—N3	0.20 (13)
N2—N1—C5—C4	−0.24 (17)	C5—N1—C9—N4	−0.30 (17)
C9—N1—C5—C4	178.93 (10)	N2—N1—C9—N4	178.99 (10)
C3—C4—C5—N1	−76.46 (13)	N1—N2—C10—N5	−176.45 (10)
C3—C4—C5—C6	102.41 (13)	N1—N2—C10—N3	0.56 (13)
N1—C5—C6—C7	0.35 (16)	C9—N3—C10—N2	−0.45 (13)
C4—C5—C6—C7	−178.55 (11)	C9—N3—C10—N5	176.55 (10)
C9—N4—C7—C6	0.00 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H1···N2ⁱ	0.88 (1)	2.24 (1)	3.095 (1)	166 (2)
N5—H2···N3ⁱⁱ	0.89 (1)	2.15 (1)	3.037 (2)	175 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₃N₅O₂
M_r	235.25
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	22.9635 (4), 7.7447 (1), 14.7017 (3)
β (°)	124.574 (1)
V (Å³)	2152.87 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.32 × 0.21 × 0.20

Data collection
Diffractometer	Bruker APEX DUO diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	21320, 4613, 3058
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.801

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.138, 1.02
No. of reflections	4613
No. of parameters	163
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.32

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H1···N2ⁱ	0.88 (1)	2.24 (1)	3.095 (1)	166 (2)
N5—H2···N3ⁱⁱ	0.89 (1)	2.15 (1)	3.037 (2)	175 (2)

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

Acknowledgements

We thank Université Mohammed V-Agdal and the University of Malaya for supporting this study.

References

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