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

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

doi:10.1107/S160053680903133X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2152

doi:10.1107/S160053680903133X

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

Redwan Mohamed Zemama,^a Ibtissam Amari,^a Rachid Bouhfid,^b El Mokhtar Essassi ^a and Seik Weng Ng ^c ^*

^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, Avenue de l'Armée Royale, Madinat El Irfane, 10100 Rabat, Morocco, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 7 August 2009; accepted 8 August 2009; online 15 August 2009)

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

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

Crystal data

C₁₂H₁₅N₅O
M_r = 245.29
Monoclinic, P 2₁ /n
a = 7.4674 (3) Å
b = 8.3398 (3) Å
c = 20.2214 (6) Å
β = 95.174 (2)°
V = 1254.19 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.3 × 0.3 × 0.3 mm

Data collection

Bruker APEX2 diffractometer
Absorption correction: none
11394 measured reflections
2435 independent reflections
1600 reflections with I > 2σ(I)
R_int = 0.041

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.176
S = 1.03
2435 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.31 e Å⁻³

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903133X/xu2583sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680903133X/xu2583Isup2.hkl

checkCIF report

Related literature top

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.

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

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

C₁₂H₁₅N₅O	F(000) = 520
M_r = 245.29	D_x = 1.299 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2666 reflections
a = 7.4674 (3) Å	θ = 2.6–23.2°
b = 8.3398 (3) Å	µ = 0.09 mm⁻¹
c = 20.2214 (6) Å	T = 293 K
β = 95.174 (2)°	Block, colorless
V = 1254.19 (8) Å³	0.3 × 0.3 × 0.3 mm
Z = 4

Data collection top

Bruker APEXII diffractometer	1600 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.041
Graphite monochromator	θ_max = 25.9°, θ_min = 2.0°
ϕ and ω scans	h = −9→9
11394 measured reflections	k = −10→10
2435 independent reflections	l = −22→24

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.1011P)² + 0.1814P] where P = (F_o² + 2F_c²)/3
2435 reflections	(Δ/σ)_max = 0.001
164 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₂H₁₅N₅O	V = 1254.19 (8) Å³
M_r = 245.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.4674 (3) Å	µ = 0.09 mm⁻¹
b = 8.3398 (3) Å	T = 293 K
c = 20.2214 (6) Å	0.3 × 0.3 × 0.3 mm
β = 95.174 (2)°

Data collection top

Bruker APEXII diffractometer	1600 reflections with I > 2σ(I)
11394 measured reflections	R_int = 0.041
2435 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.03	Δρ_max = 0.62 e Å⁻³
2435 reflections	Δρ_min = −0.31 e Å⁻³
164 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.6016 (3)	0.9072 (2)	0.62240 (9)	0.0504 (5)
N1	0.6575 (3)	0.4291 (2)	0.67475 (9)	0.0372 (5)
N2	0.6714 (3)	0.4126 (2)	0.60624 (9)	0.0346 (5)
N3	0.7253 (3)	0.2937 (3)	0.51391 (10)	0.0486 (6)
N4	0.7390 (3)	0.4593 (3)	0.50437 (9)	0.0424 (6)
N5	0.7149 (3)	0.6893 (2)	0.57403 (9)	0.0360 (5)
C1	0.5941 (3)	0.7634 (3)	0.61190 (10)	0.0353 (6)
C2	0.4588 (3)	0.6533 (3)	0.63974 (10)	0.0328 (6)
H2	0.4112	0.5834	0.6033	0.039*
C3	0.3002 (3)	0.7447 (3)	0.66310 (12)	0.0460 (7)
H3A	0.3402	0.8057	0.7025	0.055*
H3B	0.2560	0.8200	0.6289	0.055*
C4	0.1488 (4)	0.6348 (4)	0.67861 (16)	0.0600 (8)
H4	0.1127	0.5587	0.6465	0.072*
C5	0.0662 (5)	0.6348 (5)	0.73019 (19)	0.0877 (12)
H5A	0.0969	0.7084	0.7639	0.105*
H5B	−0.0256	0.5613	0.7346	0.105*
C6	0.5616 (3)	0.5471 (3)	0.69075 (10)	0.0338 (6)
C7	0.5614 (4)	0.5818 (3)	0.76328 (11)	0.0480 (7)
H7A	0.6349	0.5044	0.7882	0.072*
H7B	0.4406	0.5759	0.7758	0.072*
H7C	0.6086	0.6874	0.7724	0.072*
C8	0.6870 (3)	0.2708 (3)	0.57428 (13)	0.0433 (6)
H8	0.6722	0.1707	0.5933	0.052*
C9	0.7056 (3)	0.5264 (3)	0.56022 (11)	0.0334 (6)
C10	0.8431 (3)	0.7867 (3)	0.53946 (12)	0.0449 (7)
H10A	0.9421	0.7191	0.5286	0.054*
H10B	0.8920	0.8704	0.5692	0.054*
C11	0.7587 (4)	0.8618 (3)	0.47735 (13)	0.0519 (7)
H11	0.6702	0.9388	0.4813	0.062*
C12	0.8000 (5)	0.8273 (4)	0.41876 (16)	0.0779 (11)
H12A	0.8880	0.7509	0.4130	0.093*
H12B	0.7420	0.8788	0.3820	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0657 (13)	0.0282 (11)	0.0585 (11)	−0.0048 (9)	0.0122 (9)	−0.0007 (8)
N1	0.0448 (12)	0.0352 (12)	0.0313 (10)	−0.0009 (10)	0.0013 (8)	0.0048 (8)
N2	0.0407 (12)	0.0290 (11)	0.0341 (10)	0.0007 (9)	0.0037 (8)	0.0025 (8)
N3	0.0564 (15)	0.0419 (14)	0.0482 (13)	0.0010 (11)	0.0084 (11)	−0.0081 (10)
N4	0.0485 (13)	0.0417 (13)	0.0376 (11)	−0.0001 (10)	0.0073 (9)	−0.0018 (9)
N5	0.0391 (12)	0.0314 (12)	0.0381 (10)	−0.0050 (9)	0.0063 (9)	0.0049 (8)
C1	0.0424 (15)	0.0303 (14)	0.0327 (12)	0.0003 (11)	−0.0005 (10)	0.0010 (10)
C2	0.0363 (13)	0.0296 (13)	0.0324 (12)	−0.0009 (10)	0.0016 (10)	0.0014 (9)
C3	0.0504 (17)	0.0422 (15)	0.0461 (14)	0.0071 (13)	0.0087 (12)	0.0053 (11)
C4	0.0377 (16)	0.081 (2)	0.0619 (18)	0.0146 (15)	0.0103 (13)	0.0091 (16)
C5	0.066 (2)	0.106 (3)	0.093 (3)	0.009 (2)	0.018 (2)	0.018 (2)
C6	0.0360 (14)	0.0328 (13)	0.0323 (12)	−0.0049 (11)	0.0018 (10)	0.0028 (10)
C7	0.0541 (17)	0.0556 (18)	0.0340 (13)	0.0011 (14)	0.0022 (11)	0.0019 (11)
C8	0.0489 (16)	0.0299 (14)	0.0510 (15)	0.0011 (12)	0.0038 (12)	−0.0002 (11)
C9	0.0323 (13)	0.0331 (14)	0.0342 (12)	−0.0008 (10)	0.0004 (9)	0.0016 (10)
C10	0.0443 (16)	0.0436 (16)	0.0475 (14)	−0.0111 (13)	0.0080 (12)	0.0063 (11)
C11	0.0567 (18)	0.0493 (18)	0.0519 (16)	−0.0001 (14)	0.0166 (13)	0.0142 (13)
C12	0.100 (3)	0.079 (3)	0.0560 (19)	0.009 (2)	0.0132 (18)	0.0164 (17)

Geometric parameters (Å, º) top

O1—C1	1.218 (3)	C3—H3B	0.9700
N1—C6	1.276 (3)	C4—C5	1.259 (4)
N1—N2	1.405 (3)	C4—H4	0.9300
N2—C8	1.358 (3)	C5—H5A	0.9300
N2—C9	1.369 (3)	C5—H5B	0.9300
N3—C8	1.293 (3)	C6—C7	1.495 (3)
N3—N4	1.400 (3)	C7—H7A	0.9600
N4—C9	1.304 (3)	C7—H7B	0.9600
N5—C1	1.381 (3)	C7—H7C	0.9600
N5—C9	1.388 (3)	C8—H8	0.9300
N5—C10	1.479 (3)	C10—C11	1.491 (4)
C1—C2	1.511 (3)	C10—H10A	0.9700
C2—C6	1.514 (3)	C10—H10B	0.9700
C2—C3	1.519 (3)	C11—C12	1.283 (4)
C2—H2	0.9800	C11—H11	0.9300
C3—C4	1.510 (4)	C12—H12A	0.9300
C3—H3A	0.9700	C12—H12B	0.9300

C6—N1—N2	114.74 (18)	H5A—C5—H5B	120.0
C8—N2—C9	104.5 (2)	N1—C6—C7	116.6 (2)
C8—N2—N1	124.87 (19)	N1—C6—C2	122.7 (2)
C9—N2—N1	129.60 (19)	C7—C6—C2	120.7 (2)
C8—N3—N4	107.47 (19)	C6—C7—H7A	109.5
C9—N4—N3	106.37 (19)	C6—C7—H7B	109.5
C1—N5—C9	121.80 (19)	H7A—C7—H7B	109.5
C1—N5—C10	119.9 (2)	C6—C7—H7C	109.5
C9—N5—C10	117.75 (19)	H7A—C7—H7C	109.5
O1—C1—N5	121.0 (2)	H7B—C7—H7C	109.5
O1—C1—C2	123.7 (2)	N3—C8—N2	110.9 (2)
N5—C1—C2	115.2 (2)	N3—C8—H8	124.5
C1—C2—C6	107.12 (18)	N2—C8—H8	124.5
C1—C2—C3	112.1 (2)	N4—C9—N2	110.7 (2)
C6—C2—C3	116.29 (18)	N4—C9—N5	125.7 (2)
C1—C2—H2	106.9	N2—C9—N5	123.41 (19)
C6—C2—H2	106.9	N5—C10—C11	112.7 (2)
C3—C2—H2	106.9	N5—C10—H10A	109.0
C4—C3—C2	112.3 (2)	C11—C10—H10A	109.0
C4—C3—H3A	109.1	N5—C10—H10B	109.0
C2—C3—H3A	109.1	C11—C10—H10B	109.0
C4—C3—H3B	109.1	H10A—C10—H10B	107.8
C2—C3—H3B	109.1	C12—C11—C10	124.4 (3)
H3A—C3—H3B	107.9	C12—C11—H11	117.8
C5—C4—C3	127.1 (4)	C10—C11—H11	117.8
C5—C4—H4	116.4	C11—C12—H12A	120.0
C3—C4—H4	116.4	C11—C12—H12B	120.0
C4—C5—H5A	120.0	H12A—C12—H12B	120.0
C4—C5—H5B	120.0

C6—N1—N2—C8	−147.4 (2)	C1—C2—C6—C7	101.0 (2)
C6—N1—N2—C9	46.1 (3)	C3—C2—C6—C7	−25.3 (3)
C8—N3—N4—C9	−0.7 (3)	N4—N3—C8—N2	0.8 (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—C2	3.0 (3)	N3—N4—C9—N2	0.3 (3)
C10—N5—C1—C2	174.68 (19)	N3—N4—C9—N5	176.1 (2)
O1—C1—C2—C6	−110.7 (2)	C8—N2—C9—N4	0.2 (3)
N5—C1—C2—C6	67.9 (2)	N1—N2—C9—N4	168.8 (2)
O1—C1—C2—C3	18.0 (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—C4	169.1 (2)	C1—N5—C9—N4	142.8 (2)
C6—C2—C3—C4	−67.2 (3)	C10—N5—C9—N4	−29.0 (3)
C2—C3—C4—C5	130.9 (3)	C1—N5—C9—N2	−41.9 (3)
N2—N1—C6—C7	−172.6 (2)	C10—N5—C9—N2	146.2 (2)
N2—N1—C6—C2	4.6 (3)	C1—N5—C10—C11	−78.4 (3)
C1—C2—C6—N1	−76.1 (3)	C9—N5—C10—C11	93.6 (3)
C3—C2—C6—N1	157.6 (2)	N5—C10—C11—C12	−114.4 (3)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₅N₅O
M_r	245.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.4674 (3), 8.3398 (3), 20.2214 (6)
β (°)	95.174 (2)
V (Å³)	1254.19 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.3 × 0.3 × 0.3

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11394, 2435, 1600
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.176, 1.03
No. of reflections	2435
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.31

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Acknowledgements

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

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Essassi, E. M., Lavergne, J. P. & Vialleffont, P. (1977). Tetrahedron, 33, 2807–2812. CrossRef CAS Web of Science Google Scholar
Richter, P. & Sheefelot, U. (1991). Pharmazie, 46, 701–705. PubMed CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar