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Acta Cryst. (2009). E65, o2148    [ doi:10.1107/S1600536809031341 ]

6-Methyl-7,7,9-tripropargyl-7H-1,2,4-triazolo[4,3-b][1,2,4]triazepin-8(9H)-one

R. M. Zemama, I. Amari, R. Bouhfid, E. M. Essassi and S. W. Ng

Abstract top

The title compound, C15H13N5O, features a triazolyl ring fused with a seven-membered triazepinyl ring; the latter ring adopts a boat conformation (with the propargyl-bearing C atom as the prow and the fused-ring C/N atoms as the stern).

Related literature top

Triazepines are a class of compounds used in the treatment of neuronal disorders. They are also the reactants for the synthesis of other heterocyclic compounds; see, for example: Essassi et al. (1977); Richter & Sheefelot (1991).

Experimental top

To a solution of 6-methyl-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazepin-8(9H)-one (1 g, 6 mmol) in N,N-dimethylformamide (20 ml), potassium carbonate (1.26 g, 9 mmol), propargyl bromide (0.7 ml, 9 mmol) and a catalytic amount of tetrabutyammonium broide were added. The mixture was stirred for 12 h. After the completion of the reaction (as monitored by TLC), the solid material was removed by filtration and the solvent evaporated under vacuum. Dichloromethane (20 ml) was added and the solution filtered. The solvent was removed and the product purified by column chromatography (30% ethyl acetate/hexane) to afford colorless crystals in 15% yield; m.p. 463 K. The formulation was established by proton and carbon-13 NMR spectroscopy in DMSO-d6.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the refinement in the riding model approximation, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the others.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C15H13N5O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
6-Methyl-7,7,9-tripropargyl-7H-1,2,4- triazolo[4,3-b][1,2,4]triazepin-8(9H)-one top
Crystal data top
C15H13N5OZ = 2
Mr = 279.30F(000) = 292
Triclinic, P1Dx = 1.333 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.6710 (2) ÅCell parameters from 6818 reflections
b = 8.2415 (2) Åθ = 2.8–32.3°
c = 12.9619 (3) ŵ = 0.09 mm−1
α = 108.510 (1)°T = 293 K
β = 90.659 (1)°Block, colorless
γ = 114.726 (1)°0.3 × 0.3 × 0.3 mm
V = 695.85 (3) Å3
Data collection top
Bruker APEX2
diffractometer		2577 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.026
graphiteθmax = 27.5°, θmin = 1.7°
φ and ω scansh = −9→9
16879 measured reflectionsk = −10→10
3187 independent reflectionsl = −16→16
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0758P)2 + 0.0861P]
where P = (Fo2 + 2Fc2)/3
3187 reflections(Δ/σ)max = 0.001
191 parametersΔρmax = 0.33 e Å−3
0 restraintsΔρmin = −0.26 e Å−3
Crystal data top
C15H13N5Oγ = 114.726 (1)°
Mr = 279.30V = 695.85 (3) Å3
Triclinic, P1Z = 2
a = 7.6710 (2) ÅMo Kα radiation
b = 8.2415 (2) ŵ = 0.09 mm−1
c = 12.9619 (3) ÅT = 293 K
α = 108.510 (1)°0.3 × 0.3 × 0.3 mm
β = 90.659 (1)°
Data collection top
Bruker APEX2
diffractometer		Rint = 0.026
16879 measured reflectionsθmax = 27.5°
3187 independent reflectionsStandard reflections: 0
2577 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.129Δρmax = 0.33 e Å−3
S = 1.06Δρmin = −0.26 e Å−3
3187 reflectionsAbsolute structure: ?
191 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.30213 (18)0.47985 (14)0.37303 (8)0.0488 (3)
N10.07241 (16)−0.03916 (15)0.11746 (9)0.0346 (3)
N20.22767 (16)0.05768 (15)0.07150 (8)0.0323 (3)
N30.4030 (2)0.1070 (2)−0.05735 (10)0.0462 (3)
N40.46123 (19)0.28152 (18)0.02864 (10)0.0446 (3)
N50.35151 (17)0.38407 (15)0.19840 (9)0.0372 (3)
C10.31447 (19)0.35728 (17)0.29631 (11)0.0330 (3)
C20.28282 (18)0.16329 (17)0.30330 (10)0.0289 (3)
C30.09422 (18)0.01262 (17)0.22312 (10)0.0303 (3)
C4−0.0871 (2)−0.0827 (2)0.26582 (13)0.0475 (4)
H4A−0.1893−0.17480.20490.071*
H4B−0.12550.01140.30900.071*
H4C−0.0628−0.14610.31090.071*
C50.45567 (18)0.11327 (18)0.27425 (11)0.0317 (3)
H5A0.45020.01910.30550.038*
H5B0.44000.05600.19470.038*
C60.6465 (2)0.2779 (2)0.31450 (12)0.0412 (3)
C70.8004 (3)0.4075 (3)0.34405 (18)0.0702 (5)
H70.92330.51090.36760.084*
C80.2658 (2)0.18290 (19)0.42552 (11)0.0372 (3)
H8A0.37960.29440.47280.045*
H8B0.15250.20370.44310.045*
C90.2492 (2)0.0156 (2)0.44969 (11)0.0398 (3)
C100.2456 (2)−0.1166 (2)0.46867 (14)0.0512 (4)
H100.2427−0.22080.48360.061*
C110.2649 (2)−0.0213 (2)−0.03028 (11)0.0401 (3)
H110.1996−0.1499−0.07420.048*
C120.3531 (2)0.24704 (19)0.10322 (11)0.0343 (3)
C130.3765 (2)0.56697 (19)0.18940 (13)0.0451 (4)
H13A0.44270.67000.25930.054*
H13B0.45640.59330.13380.054*
C140.1885 (3)0.5585 (2)0.15971 (13)0.0482 (4)
C150.0358 (3)0.5466 (3)0.13320 (17)0.0655 (5)
H15−0.08530.53720.11220.079*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0733 (8)0.0385 (5)0.0407 (6)0.0331 (5)0.0150 (5)0.0102 (4)
N10.0306 (6)0.0390 (6)0.0356 (6)0.0150 (5)0.0058 (4)0.0157 (5)
N20.0347 (6)0.0390 (6)0.0276 (5)0.0190 (5)0.0069 (4)0.0138 (4)
N30.0575 (8)0.0644 (8)0.0371 (6)0.0405 (7)0.0202 (6)0.0246 (6)
N40.0528 (8)0.0531 (7)0.0458 (7)0.0315 (6)0.0235 (6)0.0285 (6)
N50.0478 (7)0.0324 (5)0.0395 (6)0.0214 (5)0.0155 (5)0.0180 (5)
C10.0355 (7)0.0307 (6)0.0346 (7)0.0165 (5)0.0079 (5)0.0114 (5)
C20.0318 (6)0.0302 (6)0.0278 (6)0.0156 (5)0.0082 (5)0.0116 (5)
C30.0293 (6)0.0325 (6)0.0341 (7)0.0158 (5)0.0069 (5)0.0152 (5)
C40.0324 (7)0.0619 (9)0.0511 (9)0.0162 (7)0.0116 (6)0.0301 (8)
C50.0315 (6)0.0366 (6)0.0311 (6)0.0180 (5)0.0071 (5)0.0132 (5)
C60.0358 (7)0.0486 (8)0.0410 (8)0.0188 (6)0.0084 (6)0.0182 (6)
C70.0408 (10)0.0661 (11)0.0781 (13)0.0050 (8)0.0039 (9)0.0197 (10)
C80.0454 (8)0.0416 (7)0.0290 (6)0.0224 (6)0.0112 (6)0.0138 (5)
C90.0400 (7)0.0508 (8)0.0310 (7)0.0195 (6)0.0083 (6)0.0183 (6)
C100.0515 (9)0.0566 (9)0.0538 (9)0.0225 (8)0.0074 (7)0.0319 (8)
C110.0478 (8)0.0517 (8)0.0295 (7)0.0313 (7)0.0066 (6)0.0129 (6)
C120.0390 (7)0.0390 (7)0.0361 (7)0.0224 (6)0.0122 (5)0.0204 (6)
C130.0548 (9)0.0323 (7)0.0539 (9)0.0186 (6)0.0167 (7)0.0236 (6)
C140.0677 (11)0.0368 (7)0.0506 (9)0.0289 (7)0.0161 (8)0.0208 (7)
C150.0762 (13)0.0636 (11)0.0728 (12)0.0435 (10)0.0109 (10)0.0274 (10)
Geometric parameters (Å, °) top
O1—C11.2094 (15)C4—H4C0.9600
N1—C31.2845 (17)C5—C61.4583 (19)
N1—N21.3905 (15)C5—H5A0.9700
N2—C121.3630 (17)C5—H5B0.9700
N2—C111.3653 (17)C6—C71.165 (2)
N3—C111.293 (2)C7—H70.9300
N3—N41.3940 (18)C8—C91.4643 (19)
N4—C121.3035 (17)C8—H8A0.9700
N5—C11.3690 (17)C8—H8B0.9700
N5—C121.3874 (17)C9—C101.180 (2)
N5—C131.4808 (16)C10—H100.9300
C1—C21.5463 (16)C11—H110.9300
C2—C31.5357 (17)C13—C141.455 (2)
C2—C81.5532 (17)C13—H13A0.9700
C2—C51.5620 (17)C13—H13B0.9700
C3—C41.4957 (19)C14—C151.172 (3)
C4—H4A0.9600C15—H150.9300
C4—H4B0.9600
C3—N1—N2117.64 (11)C2—C5—H5A108.8
C12—N2—C11104.18 (11)C6—C5—H5B108.8
C12—N2—N1130.86 (11)C2—C5—H5B108.8
C11—N2—N1124.18 (11)H5A—C5—H5B107.7
C11—N3—N4107.51 (11)C7—C6—C5178.18 (18)
C12—N4—N3106.47 (12)C6—C7—H7180.0
C1—N5—C12124.97 (10)C9—C8—C2113.42 (11)
C1—N5—C13118.17 (11)C9—C8—H8A108.9
C12—N5—C13116.66 (11)C2—C8—H8A108.9
O1—C1—N5120.67 (11)C9—C8—H8B108.9
O1—C1—C2121.75 (12)C2—C8—H8B108.9
N5—C1—C2117.55 (10)H8A—C8—H8B107.7
C3—C2—C1106.03 (10)C10—C9—C8176.60 (16)
C3—C2—C8112.84 (10)C9—C10—H10180.0
C1—C2—C8105.71 (10)N3—C11—N2110.81 (13)
C3—C2—C5110.77 (10)N3—C11—H11124.6
C1—C2—C5113.58 (10)N2—C11—H11124.6
C8—C2—C5107.91 (10)N4—C12—N2111.01 (12)
N1—C3—C4113.98 (12)N4—C12—N5125.45 (12)
N1—C3—C2125.47 (11)N2—C12—N5123.34 (11)
C4—C3—C2120.51 (11)C14—C13—N5110.59 (12)
C3—C4—H4A109.5C14—C13—H13A109.5
C3—C4—H4B109.5N5—C13—H13A109.5
H4A—C4—H4B109.5C14—C13—H13B109.5
C3—C4—H4C109.5N5—C13—H13B109.5
H4A—C4—H4C109.5H13A—C13—H13B108.1
H4B—C4—H4C109.5C15—C14—C13178.00 (18)
C6—C5—C2113.64 (11)C14—C15—H15180.0
C6—C5—H5A108.8
C3—N1—N2—C12−40.63 (18)C1—C2—C5—C637.77 (15)
C3—N1—N2—C11151.13 (13)C8—C2—C5—C6−79.06 (13)
C11—N3—N4—C120.01 (16)C3—C2—C8—C968.72 (15)
C12—N5—C1—O1−174.64 (13)C1—C2—C8—C9−175.83 (11)
C13—N5—C1—O10.2 (2)C5—C2—C8—C9−53.99 (15)
C12—N5—C1—C23.4 (2)C2—C8—C9—C1072 (3)
C13—N5—C1—C2178.27 (11)N4—N3—C11—N2−0.81 (16)
O1—C1—C2—C3112.39 (14)C12—N2—C11—N31.25 (15)
N5—C1—C2—C3−65.67 (14)N1—N2—C11—N3172.10 (11)
O1—C1—C2—C8−7.63 (17)N3—N4—C12—N20.80 (15)
N5—C1—C2—C8174.31 (12)N3—N4—C12—N5−174.12 (12)
O1—C1—C2—C5−125.74 (14)C11—N2—C12—N4−1.25 (15)
N5—C1—C2—C556.20 (15)N1—N2—C12—N4−171.23 (12)
N2—N1—C3—C4173.10 (11)C11—N2—C12—N5173.80 (12)
N2—N1—C3—C2−4.67 (18)N1—N2—C12—N53.8 (2)
C1—C2—C3—N168.84 (15)C1—N5—C12—N4−148.84 (14)
C8—C2—C3—N1−175.91 (12)C13—N5—C12—N436.3 (2)
C5—C2—C3—N1−54.80 (16)C1—N5—C12—N236.8 (2)
C1—C2—C3—C4−108.79 (13)C13—N5—C12—N2−138.05 (13)
C8—C2—C3—C46.46 (16)C1—N5—C13—C14−84.87 (17)
C5—C2—C3—C4127.57 (13)C12—N5—C13—C1490.39 (15)
C3—C2—C5—C6156.96 (11)
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 (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Essassi, E. M., Lavergne, J. P. & Vialleffont, P. (1977). Tetrahedron, 33, 2807–2812.

Richter, P. & Sheefelot, U. (1991). Pharmazie, 46, 701–705.

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

Westrip, S. P. (2009). publCIF. In preparation.