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Acta Cryst. (2009). E65, o2152    [ doi:10.1107/S160053680903133X ]

7,9-Diallyl-6-methyl-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, C12H15N5O, features a triazolyl ring fused with a seven-membered triazepinyl ring; the latter ring adopts a boat conformation with the allyl-bearing C atom as the prow and the C and N fused-ring atoms as the stern.

Related literature top

Triazepines are 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), allyl bromide (0.8 ml, 9 mmol) and a catalytic amount of tetrabutyammonium bromide 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 30% yield; m.p. 423 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 U(H) set to 1.2U(C).

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 C12H15N5O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
7,9-Diallyl-6-methyl-7H-1,2,4-triazolo[4,3-b][1,2,4]triazepin-\ 8(9H)-one top
Crystal data top
C12H15N5OF(000) = 520
Mr = 245.29Dx = 1.299 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2666 reflections
a = 7.4674 (3) Åθ = 2.6–23.2°
b = 8.3398 (3) ŵ = 0.09 mm−1
c = 20.2214 (6) ÅT = 293 K
β = 95.174 (2)°Block, colorless
V = 1254.19 (8) Å30.3 × 0.3 × 0.3 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer		1600 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.041
graphiteθmax = 25.9°, θmin = 2.0°
φ and ω scansh = −9→9
11394 measured reflectionsk = −10→10
2435 independent reflectionsl = −22→24
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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.176H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.1011P)2 + 0.1814P]
where P = (Fo2 + 2Fc2)/3
2435 reflections(Δ/σ)max = 0.001
164 parametersΔρmax = 0.62 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C12H15N5OV = 1254.19 (8) Å3
Mr = 245.29Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.4674 (3) ŵ = 0.09 mm−1
b = 8.3398 (3) ÅT = 293 K
c = 20.2214 (6) Å0.3 × 0.3 × 0.3 mm
β = 95.174 (2)°
Data collection top
Bruker APEXII
diffractometer		Rint = 0.041
11394 measured reflectionsθmax = 25.9°
2435 independent reflectionsStandard reflections: 0
1600 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.176Δρmax = 0.62 e Å−3
S = 1.03Δρmin = −0.31 e Å−3
2435 reflectionsAbsolute structure: ?
164 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.6016 (3)0.9072 (2)0.62240 (9)0.0504 (5)
N10.6575 (3)0.4291 (2)0.67475 (9)0.0372 (5)
N20.6714 (3)0.4126 (2)0.60624 (9)0.0346 (5)
N30.7253 (3)0.2937 (3)0.51391 (10)0.0486 (6)
N40.7390 (3)0.4593 (3)0.50437 (9)0.0424 (6)
N50.7149 (3)0.6893 (2)0.57403 (9)0.0360 (5)
C10.5941 (3)0.7634 (3)0.61190 (10)0.0353 (6)
C20.4588 (3)0.6533 (3)0.63974 (10)0.0328 (6)
H20.41120.58340.60330.039*
C30.3002 (3)0.7447 (3)0.66310 (12)0.0460 (7)
H3A0.34020.80570.70250.055*
H3B0.25600.82000.62890.055*
C40.1488 (4)0.6348 (4)0.67861 (16)0.0600 (8)
H40.11270.55870.64650.072*
C50.0662 (5)0.6348 (5)0.73019 (19)0.0877 (12)
H5A0.09690.70840.76390.105*
H5B−0.02560.56130.73460.105*
C60.5616 (3)0.5471 (3)0.69075 (10)0.0338 (6)
C70.5614 (4)0.5818 (3)0.76328 (11)0.0480 (7)
H7A0.63490.50440.78820.072*
H7B0.44060.57590.77580.072*
H7C0.60860.68740.77240.072*
C80.6870 (3)0.2708 (3)0.57428 (13)0.0433 (6)
H80.67220.17070.59330.052*
C90.7056 (3)0.5264 (3)0.56022 (11)0.0334 (6)
C100.8431 (3)0.7867 (3)0.53946 (12)0.0449 (7)
H10A0.94210.71910.52860.054*
H10B0.89200.87040.56920.054*
C110.7587 (4)0.8618 (3)0.47735 (13)0.0519 (7)
H110.67020.93880.48130.062*
C120.8000 (5)0.8273 (4)0.41876 (16)0.0779 (11)
H12A0.88800.75090.41300.093*
H12B0.74200.87880.38200.093*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0657 (13)0.0282 (11)0.0585 (11)−0.0048 (9)0.0122 (9)−0.0007 (8)
N10.0448 (12)0.0352 (12)0.0313 (10)−0.0009 (10)0.0013 (8)0.0048 (8)
N20.0407 (12)0.0290 (11)0.0341 (10)0.0007 (9)0.0037 (8)0.0025 (8)
N30.0564 (15)0.0419 (14)0.0482 (13)0.0010 (11)0.0084 (11)−0.0081 (10)
N40.0485 (13)0.0417 (13)0.0376 (11)−0.0001 (10)0.0073 (9)−0.0018 (9)
N50.0391 (12)0.0314 (12)0.0381 (10)−0.0050 (9)0.0063 (9)0.0049 (8)
C10.0424 (15)0.0303 (14)0.0327 (12)0.0003 (11)−0.0005 (10)0.0010 (10)
C20.0363 (13)0.0296 (13)0.0324 (12)−0.0009 (10)0.0016 (10)0.0014 (9)
C30.0504 (17)0.0422 (15)0.0461 (14)0.0071 (13)0.0087 (12)0.0053 (11)
C40.0377 (16)0.081 (2)0.0619 (18)0.0146 (15)0.0103 (13)0.0091 (16)
C50.066 (2)0.106 (3)0.093 (3)0.009 (2)0.018 (2)0.018 (2)
C60.0360 (14)0.0328 (13)0.0323 (12)−0.0049 (11)0.0018 (10)0.0028 (10)
C70.0541 (17)0.0556 (18)0.0340 (13)0.0011 (14)0.0022 (11)0.0019 (11)
C80.0489 (16)0.0299 (14)0.0510 (15)0.0011 (12)0.0038 (12)−0.0002 (11)
C90.0323 (13)0.0331 (14)0.0342 (12)−0.0008 (10)0.0004 (9)0.0016 (10)
C100.0443 (16)0.0436 (16)0.0475 (14)−0.0111 (13)0.0080 (12)0.0063 (11)
C110.0567 (18)0.0493 (18)0.0519 (16)−0.0001 (14)0.0166 (13)0.0142 (13)
C120.100 (3)0.079 (3)0.0560 (19)0.009 (2)0.0132 (18)0.0164 (17)
Geometric parameters (Å, °) top
O1—C11.218 (3)C3—H3B0.9700
N1—C61.276 (3)C4—C51.259 (4)
N1—N21.405 (3)C4—H40.9300
N2—C81.358 (3)C5—H5A0.9300
N2—C91.369 (3)C5—H5B0.9300
N3—C81.293 (3)C6—C71.495 (3)
N3—N41.400 (3)C7—H7A0.9600
N4—C91.304 (3)C7—H7B0.9600
N5—C11.381 (3)C7—H7C0.9600
N5—C91.388 (3)C8—H80.9300
N5—C101.479 (3)C10—C111.491 (4)
C1—C21.511 (3)C10—H10A0.9700
C2—C61.514 (3)C10—H10B0.9700
C2—C31.519 (3)C11—C121.283 (4)
C2—H20.9800C11—H110.9300
C3—C41.510 (4)C12—H12A0.9300
C3—H3A0.9700C12—H12B0.9300
C6—N1—N2114.74 (18)H5A—C5—H5B120.0
C8—N2—C9104.5 (2)N1—C6—C7116.6 (2)
C8—N2—N1124.87 (19)N1—C6—C2122.7 (2)
C9—N2—N1129.60 (19)C7—C6—C2120.7 (2)
C8—N3—N4107.47 (19)C6—C7—H7A109.5
C9—N4—N3106.37 (19)C6—C7—H7B109.5
C1—N5—C9121.80 (19)H7A—C7—H7B109.5
C1—N5—C10119.9 (2)C6—C7—H7C109.5
C9—N5—C10117.75 (19)H7A—C7—H7C109.5
O1—C1—N5121.0 (2)H7B—C7—H7C109.5
O1—C1—C2123.7 (2)N3—C8—N2110.9 (2)
N5—C1—C2115.2 (2)N3—C8—H8124.5
C1—C2—C6107.12 (18)N2—C8—H8124.5
C1—C2—C3112.1 (2)N4—C9—N2110.7 (2)
C6—C2—C3116.29 (18)N4—C9—N5125.7 (2)
C1—C2—H2106.9N2—C9—N5123.41 (19)
C6—C2—H2106.9N5—C10—C11112.7 (2)
C3—C2—H2106.9N5—C10—H10A109.0
C4—C3—C2112.3 (2)C11—C10—H10A109.0
C4—C3—H3A109.1N5—C10—H10B109.0
C2—C3—H3A109.1C11—C10—H10B109.0
C4—C3—H3B109.1H10A—C10—H10B107.8
C2—C3—H3B109.1C12—C11—C10124.4 (3)
H3A—C3—H3B107.9C12—C11—H11117.8
C5—C4—C3127.1 (4)C10—C11—H11117.8
C5—C4—H4116.4C11—C12—H12A120.0
C3—C4—H4116.4C11—C12—H12B120.0
C4—C5—H5A120.0H12A—C12—H12B120.0
C4—C5—H5B120.0
C6—N1—N2—C8−147.4 (2)C1—C2—C6—C7101.0 (2)
C6—N1—N2—C946.1 (3)C3—C2—C6—C7−25.3 (3)
C8—N3—N4—C9−0.7 (3)N4—N3—C8—N20.8 (3)
C9—N5—C1—O1−178.4 (2)C9—N2—C8—N3−0.6 (3)
C10—N5—C1—O1−6.7 (3)N1—N2—C8—N3−170.0 (2)
C9—N5—C1—C23.0 (3)N3—N4—C9—N20.3 (3)
C10—N5—C1—C2174.68 (19)N3—N4—C9—N5176.1 (2)
O1—C1—C2—C6−110.7 (2)C8—N2—C9—N40.2 (3)
N5—C1—C2—C667.9 (2)N1—N2—C9—N4168.8 (2)
O1—C1—C2—C318.0 (3)C8—N2—C9—N5−175.7 (2)
N5—C1—C2—C3−163.40 (19)N1—N2—C9—N5−7.1 (4)
C1—C2—C3—C4169.1 (2)C1—N5—C9—N4142.8 (2)
C6—C2—C3—C4−67.2 (3)C10—N5—C9—N4−29.0 (3)
C2—C3—C4—C5130.9 (3)C1—N5—C9—N2−41.9 (3)
N2—N1—C6—C7−172.6 (2)C10—N5—C9—N2146.2 (2)
N2—N1—C6—C24.6 (3)C1—N5—C10—C11−78.4 (3)
C1—C2—C6—N1−76.1 (3)C9—N5—C10—C1193.6 (3)
C3—C2—C6—N1157.6 (2)N5—C10—C11—C12−114.4 (3)
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.