supplementary materials


xu5412 scheme

Acta Cryst. (2012). E68, o239    [ doi:10.1107/S1600536811054468 ]

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

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

Abstract top

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.

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.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C–H 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5U(C).

The amino H-atoms were located in a difference Fourier map, and were refined with a distance restraint of N–H 0.88±0.01 Å; their temperature factors were refined.

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
[Figure 1] 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
C10H13N5O2F(000) = 992
Mr = 235.25Dx = 1.452 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3608 reflections
a = 22.9635 (4) Åθ = 2.8–35.5°
b = 7.7447 (1) ŵ = 0.11 mm1
c = 14.7017 (3) ÅT = 293 K
β = 124.574 (1)°Prism, colorless
V = 2152.87 (6) Å30.32 × 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 tubeRint = 0.050
graphiteθmax = 34.7°, θmin = 2.8°
ω scansh = 3536
21320 measured reflectionsk = 129
4613 independent reflectionsl = 2322
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0666P)2 + 0.6364P]
where P = (Fo2 + 2Fc2)/3
4613 reflections(Δ/σ)max = 0.001
163 parametersΔρmax = 0.50 e Å3
2 restraintsΔρmin = 0.32 e Å3
Crystal data top
C10H13N5O2V = 2152.87 (6) Å3
Mr = 235.25Z = 8
Monoclinic, C2/cMo Kα radiation
a = 22.9635 (4) ŵ = 0.11 mm1
b = 7.7447 (1) ÅT = 293 K
c = 14.7017 (3) Å0.32 × 0.21 × 0.20 mm
β = 124.574 (1)°
Data collection top
Bruker APEX DUO
diffractometer
Rint = 0.050
21320 measured reflectionsθmax = 34.7°
4613 independent reflectionsStandard reflections: 0
3058 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.138Δρmax = 0.50 e Å3
S = 1.02Δρmin = 0.32 e Å3
4613 reflectionsAbsolute structure: ?
163 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.66634 (4)0.58516 (12)0.48590 (7)0.01669 (18)
O20.59517 (5)0.70201 (15)0.31780 (7)0.0279 (2)
N10.60826 (5)0.99885 (13)0.53229 (7)0.01076 (18)
N20.67164 (5)0.93485 (13)0.61966 (7)0.01190 (18)
N30.66734 (5)1.23064 (13)0.63055 (8)0.01260 (19)
N40.55068 (5)1.27125 (14)0.46404 (8)0.01363 (19)
N50.77145 (5)1.08068 (14)0.76545 (8)0.0147 (2)
C10.77877 (6)0.45604 (19)0.56140 (11)0.0200 (3)
H1A0.81240.41830.54660.030*
H1B0.76460.35960.58560.030*
H1C0.80000.54270.61810.030*
C20.71486 (6)0.53072 (18)0.45759 (10)0.0177 (2)
H2A0.72840.62840.43210.021*
H2B0.69280.44450.39950.021*
C30.60866 (6)0.66849 (16)0.40788 (9)0.0151 (2)
C40.56130 (6)0.71606 (16)0.44533 (9)0.0140 (2)
H4A0.51500.66490.39550.017*
H4B0.58110.66940.51860.017*
C50.55386 (5)0.90755 (15)0.44764 (9)0.0118 (2)
C60.49644 (6)1.00289 (16)0.36969 (9)0.0133 (2)
H60.45730.94790.30990.016*
C70.49650 (6)1.18385 (16)0.37998 (9)0.0135 (2)
C80.43393 (6)1.28736 (18)0.29316 (10)0.0188 (2)
H8A0.43751.40290.31950.028*
H8B0.39121.23490.27730.028*
H8C0.43311.29040.22710.028*
C90.60642 (6)1.17669 (15)0.54011 (9)0.0114 (2)
C100.70439 (6)1.08132 (15)0.67461 (9)0.0115 (2)
H10.7866 (9)1.1735 (16)0.8069 (12)0.027 (4)*
H20.7920 (8)0.9812 (15)0.7978 (13)0.027 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0130 (4)0.0209 (5)0.0142 (4)0.0049 (3)0.0066 (3)0.0026 (3)
O20.0328 (5)0.0336 (6)0.0165 (4)0.0168 (5)0.0135 (4)0.0082 (4)
N10.0087 (4)0.0096 (4)0.0101 (4)0.0000 (3)0.0030 (3)0.0006 (3)
N20.0087 (4)0.0104 (5)0.0101 (4)0.0000 (3)0.0015 (3)0.0003 (3)
N30.0108 (4)0.0102 (4)0.0118 (4)0.0001 (3)0.0034 (3)0.0002 (3)
N40.0108 (4)0.0114 (5)0.0145 (4)0.0010 (3)0.0047 (3)0.0007 (4)
N50.0122 (4)0.0110 (5)0.0113 (4)0.0002 (4)0.0009 (3)0.0004 (4)
C10.0147 (5)0.0207 (6)0.0225 (6)0.0038 (4)0.0094 (4)0.0025 (5)
C20.0178 (5)0.0181 (6)0.0180 (5)0.0034 (5)0.0106 (4)0.0006 (5)
C30.0148 (5)0.0116 (5)0.0138 (5)0.0009 (4)0.0050 (4)0.0017 (4)
C40.0118 (4)0.0102 (5)0.0153 (5)0.0013 (4)0.0049 (4)0.0020 (4)
C50.0093 (4)0.0116 (5)0.0116 (4)0.0015 (4)0.0043 (4)0.0025 (4)
C60.0091 (4)0.0140 (5)0.0115 (4)0.0001 (4)0.0028 (4)0.0016 (4)
C70.0100 (4)0.0147 (6)0.0125 (4)0.0007 (4)0.0044 (4)0.0003 (4)
C80.0122 (5)0.0170 (6)0.0178 (5)0.0039 (4)0.0028 (4)0.0027 (5)
C90.0113 (4)0.0087 (5)0.0124 (4)0.0004 (4)0.0057 (4)0.0000 (4)
C100.0112 (4)0.0107 (5)0.0104 (4)0.0007 (4)0.0048 (4)0.0001 (4)
Geometric parameters (Å, °) top
O1—C31.3276 (14)C1—H1B0.9600
O1—C21.4555 (15)C1—H1C0.9600
O2—C31.2049 (15)C2—H2A0.9700
N1—C51.3582 (14)C2—H2B0.9700
N1—N21.3755 (12)C3—C41.5169 (17)
N1—C91.3847 (15)C4—C51.4954 (17)
N2—C101.3474 (15)C4—H4A0.9700
N3—C91.3374 (14)C4—H4B0.9700
N3—C101.3621 (15)C5—C61.3720 (15)
N4—C71.3373 (14)C6—C71.4096 (17)
N4—C91.3419 (14)C6—H60.9300
N5—C101.3494 (14)C7—C81.5016 (16)
N5—H10.877 (9)C8—H8A0.9600
N5—H20.887 (9)C8—H8B0.9600
C1—C21.5085 (17)C8—H8C0.9600
C1—H1A0.9600
C3—O1—C2116.37 (9)C5—C4—H4A109.4
C5—N1—N2127.13 (10)C3—C4—H4A109.4
C5—N1—C9122.57 (9)C5—C4—H4B109.4
N2—N1—C9110.30 (9)C3—C4—H4B109.4
C10—N2—N1101.03 (9)H4A—C4—H4B108.0
C9—N3—C10103.08 (10)N1—C5—C6115.69 (11)
C7—N4—C9116.18 (10)N1—C5—C4118.66 (9)
C10—N5—H1117.7 (11)C6—C5—C4125.64 (10)
C10—N5—H2119.6 (11)C5—C6—C7120.23 (10)
H1—N5—H2117.3 (15)C5—C6—H6119.9
C2—C1—H1A109.5C7—C6—H6119.9
C2—C1—H1B109.5N4—C7—C6123.11 (10)
H1A—C1—H1B109.5N4—C7—C8117.06 (11)
C2—C1—H1C109.5C6—C7—C8119.83 (10)
H1A—C1—H1C109.5C7—C8—H8A109.5
H1B—C1—H1C109.5C7—C8—H8B109.5
O1—C2—C1106.55 (10)H8A—C8—H8B109.5
O1—C2—H2A110.4C7—C8—H8C109.5
C1—C2—H2A110.4H8A—C8—H8C109.5
O1—C2—H2B110.4H8B—C8—H8C109.5
C1—C2—H2B110.4N3—C9—N4128.53 (11)
H2A—C2—H2B108.6N3—C9—N1109.22 (9)
O2—C3—O1124.23 (11)N4—C9—N1122.23 (10)
O2—C3—C4123.83 (11)N2—C10—N5121.70 (10)
O1—C3—C4111.95 (10)N2—C10—N3116.37 (9)
C5—C4—C3111.33 (10)N5—C10—N3121.86 (10)
C5—N1—N2—C10178.81 (11)C9—N4—C7—C8179.26 (11)
C9—N1—N2—C100.44 (12)C5—C6—C7—N40.35 (18)
C3—O1—C2—C1174.51 (11)C5—C6—C7—C8178.90 (11)
C2—O1—C3—O20.81 (19)C10—N3—C9—N4178.56 (12)
C2—O1—C3—C4178.92 (10)C10—N3—C9—N10.13 (12)
O2—C3—C4—C562.89 (16)C7—N4—C9—N3178.85 (11)
O1—C3—C4—C5117.38 (11)C7—N4—C9—N10.31 (16)
N2—N1—C5—C6179.22 (10)C5—N1—C9—N3179.09 (10)
C9—N1—C5—C60.05 (16)N2—N1—C9—N30.20 (13)
N2—N1—C5—C40.24 (17)C5—N1—C9—N40.30 (17)
C9—N1—C5—C4178.93 (10)N2—N1—C9—N4178.99 (10)
C3—C4—C5—N176.46 (13)N1—N2—C10—N5176.45 (10)
C3—C4—C5—C6102.41 (13)N1—N2—C10—N30.56 (13)
N1—C5—C6—C70.35 (16)C9—N3—C10—N20.45 (13)
C4—C5—C6—C7178.55 (11)C9—N3—C10—N5176.55 (10)
C9—N4—C7—C60.00 (17)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N5—H1···N2i0.88 (1)2.24 (1)3.095 (1)166 (2)
N5—H2···N3ii0.89 (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.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
N5—H1···N2i0.88 (1)2.24 (1)3.095 (1)166 (2)
N5—H2···N3ii0.89 (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 top

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

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Fettouhi, M., Boukhari, A., El Otmani, B. & Essassi, E. M. (1996). Acta Cryst. C52, 1031–1032.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.