6-Methyl-7,7,9-tripropargyl-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/S1600536809031341

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2148

doi:10.1107/S1600536809031341

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6-Methyl-7,7,9-tripropargyl-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, 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

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

Crystal data

C₁₅H₁₃N₅O
M_r = 279.30
Triclinic, $[P \overline 1]$
a = 7.6710 (2) Å
b = 8.2415 (2) Å
c = 12.9619 (3) Å
α = 108.510 (1)°
β = 90.659 (1)°
γ = 114.726 (1)°
V = 695.85 (3) Å³
Z = 2
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
16879 measured reflections
3187 independent reflections
2577 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.129
S = 1.06
3187 reflections
191 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.26 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/S1600536809031341/xu2584sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809031341/xu2584Isup2.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), 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.

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 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

C₁₅H₁₃N₅O	Z = 2
M_r = 279.30	F(000) = 292
Triclinic, P1	D_x = 1.333 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6710 (2) Å	Cell parameters from 6818 reflections
b = 8.2415 (2) Å	θ = 2.8–32.3°
c = 12.9619 (3) Å	µ = 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 tube	R_int = 0.026
Graphite monochromator	θ_max = 27.5°, θ_min = 1.7°
ϕ and ω scans	h = −9→9
16879 measured reflections	k = −10→10
3187 independent reflections	l = −16→16

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0758P)² + 0.0861P] where P = (F_o² + 2F_c²)/3
3187 reflections	(Δ/σ)_max = 0.001
191 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₅H₁₃N₅O	γ = 114.726 (1)°
M_r = 279.30	V = 695.85 (3) Å³
Triclinic, P1	Z = 2
a = 7.6710 (2) Å	Mo Kα radiation
b = 8.2415 (2) Å	µ = 0.09 mm⁻¹
c = 12.9619 (3) Å	T = 293 K
α = 108.510 (1)°	0.3 × 0.3 × 0.3 mm
β = 90.659 (1)°

Data collection top

Bruker APEX2 diffractometer	2577 reflections with I > 2σ(I)
16879 measured reflections	R_int = 0.026
3187 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.06	Δρ_max = 0.33 e Å⁻³
3187 reflections	Δρ_min = −0.26 e Å⁻³
191 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.30213 (18)	0.47985 (14)	0.37303 (8)	0.0488 (3)
N1	0.07241 (16)	−0.03916 (15)	0.11746 (9)	0.0346 (3)
N2	0.22767 (16)	0.05768 (15)	0.07150 (8)	0.0323 (3)
N3	0.4030 (2)	0.1070 (2)	−0.05735 (10)	0.0462 (3)
N4	0.46123 (19)	0.28152 (18)	0.02864 (10)	0.0446 (3)
N5	0.35151 (17)	0.38407 (15)	0.19840 (9)	0.0372 (3)
C1	0.31447 (19)	0.35728 (17)	0.29631 (11)	0.0330 (3)
C2	0.28282 (18)	0.16329 (17)	0.30330 (10)	0.0289 (3)
C3	0.09422 (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	−0.1748	0.2049	0.071*
H4B	−0.1255	0.0114	0.3090	0.071*
H4C	−0.0628	−0.1461	0.3109	0.071*
C5	0.45567 (18)	0.11327 (18)	0.27425 (11)	0.0317 (3)
H5A	0.4502	0.0191	0.3055	0.038*
H5B	0.4400	0.0560	0.1947	0.038*
C6	0.6465 (2)	0.2779 (2)	0.31450 (12)	0.0412 (3)
C7	0.8004 (3)	0.4075 (3)	0.34405 (18)	0.0702 (5)
H7	0.9233	0.5109	0.3676	0.084*
C8	0.2658 (2)	0.18290 (19)	0.42552 (11)	0.0372 (3)
H8A	0.3796	0.2944	0.4728	0.045*
H8B	0.1525	0.2037	0.4431	0.045*
C9	0.2492 (2)	0.0156 (2)	0.44969 (11)	0.0398 (3)
C10	0.2456 (2)	−0.1166 (2)	0.46867 (14)	0.0512 (4)
H10	0.2427	−0.2208	0.4836	0.061*
C11	0.2649 (2)	−0.0213 (2)	−0.03028 (11)	0.0401 (3)
H11	0.1996	−0.1499	−0.0742	0.048*
C12	0.3531 (2)	0.24704 (19)	0.10322 (11)	0.0343 (3)
C13	0.3765 (2)	0.56697 (19)	0.18940 (13)	0.0451 (4)
H13A	0.4427	0.6700	0.2593	0.054*
H13B	0.4564	0.5933	0.1338	0.054*
C14	0.1885 (3)	0.5585 (2)	0.15971 (13)	0.0482 (4)
C15	0.0358 (3)	0.5466 (3)	0.13320 (17)	0.0655 (5)
H15	−0.0853	0.5372	0.1122	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0733 (8)	0.0385 (5)	0.0407 (6)	0.0331 (5)	0.0150 (5)	0.0102 (4)
N1	0.0306 (6)	0.0390 (6)	0.0356 (6)	0.0150 (5)	0.0058 (4)	0.0157 (5)
N2	0.0347 (6)	0.0390 (6)	0.0276 (5)	0.0190 (5)	0.0069 (4)	0.0138 (4)
N3	0.0575 (8)	0.0644 (8)	0.0371 (6)	0.0405 (7)	0.0202 (6)	0.0246 (6)
N4	0.0528 (8)	0.0531 (7)	0.0458 (7)	0.0315 (6)	0.0235 (6)	0.0285 (6)
N5	0.0478 (7)	0.0324 (5)	0.0395 (6)	0.0214 (5)	0.0155 (5)	0.0180 (5)
C1	0.0355 (7)	0.0307 (6)	0.0346 (7)	0.0165 (5)	0.0079 (5)	0.0114 (5)
C2	0.0318 (6)	0.0302 (6)	0.0278 (6)	0.0156 (5)	0.0082 (5)	0.0116 (5)
C3	0.0293 (6)	0.0325 (6)	0.0341 (7)	0.0158 (5)	0.0069 (5)	0.0152 (5)
C4	0.0324 (7)	0.0619 (9)	0.0511 (9)	0.0162 (7)	0.0116 (6)	0.0301 (8)
C5	0.0315 (6)	0.0366 (6)	0.0311 (6)	0.0180 (5)	0.0071 (5)	0.0132 (5)
C6	0.0358 (7)	0.0486 (8)	0.0410 (8)	0.0188 (6)	0.0084 (6)	0.0182 (6)
C7	0.0408 (10)	0.0661 (11)	0.0781 (13)	0.0050 (8)	0.0039 (9)	0.0197 (10)
C8	0.0454 (8)	0.0416 (7)	0.0290 (6)	0.0224 (6)	0.0112 (6)	0.0138 (5)
C9	0.0400 (7)	0.0508 (8)	0.0310 (7)	0.0195 (6)	0.0083 (6)	0.0183 (6)
C10	0.0515 (9)	0.0566 (9)	0.0538 (9)	0.0225 (8)	0.0074 (7)	0.0319 (8)
C11	0.0478 (8)	0.0517 (8)	0.0295 (7)	0.0313 (7)	0.0066 (6)	0.0129 (6)
C12	0.0390 (7)	0.0390 (7)	0.0361 (7)	0.0224 (6)	0.0122 (5)	0.0204 (6)
C13	0.0548 (9)	0.0323 (7)	0.0539 (9)	0.0186 (6)	0.0167 (7)	0.0236 (6)
C14	0.0677 (11)	0.0368 (7)	0.0506 (9)	0.0289 (7)	0.0161 (8)	0.0208 (7)
C15	0.0762 (13)	0.0636 (11)	0.0728 (12)	0.0435 (10)	0.0109 (10)	0.0274 (10)

Geometric parameters (Å, º) top

O1—C1	1.2094 (15)	C4—H4C	0.9600
N1—C3	1.2845 (17)	C5—C6	1.4583 (19)
N1—N2	1.3905 (15)	C5—H5A	0.9700
N2—C12	1.3630 (17)	C5—H5B	0.9700
N2—C11	1.3653 (17)	C6—C7	1.165 (2)
N3—C11	1.293 (2)	C7—H7	0.9300
N3—N4	1.3940 (18)	C8—C9	1.4643 (19)
N4—C12	1.3035 (17)	C8—H8A	0.9700
N5—C1	1.3690 (17)	C8—H8B	0.9700
N5—C12	1.3874 (17)	C9—C10	1.180 (2)
N5—C13	1.4808 (16)	C10—H10	0.9300
C1—C2	1.5463 (16)	C11—H11	0.9300
C2—C3	1.5357 (17)	C13—C14	1.455 (2)
C2—C8	1.5532 (17)	C13—H13A	0.9700
C2—C5	1.5620 (17)	C13—H13B	0.9700
C3—C4	1.4957 (19)	C14—C15	1.172 (3)
C4—H4A	0.9600	C15—H15	0.9300
C4—H4B	0.9600

C3—N1—N2	117.64 (11)	C2—C5—H5A	108.8
C12—N2—C11	104.18 (11)	C6—C5—H5B	108.8
C12—N2—N1	130.86 (11)	C2—C5—H5B	108.8
C11—N2—N1	124.18 (11)	H5A—C5—H5B	107.7
C11—N3—N4	107.51 (11)	C7—C6—C5	178.18 (18)
C12—N4—N3	106.47 (12)	C6—C7—H7	180.0
C1—N5—C12	124.97 (10)	C9—C8—C2	113.42 (11)
C1—N5—C13	118.17 (11)	C9—C8—H8A	108.9
C12—N5—C13	116.66 (11)	C2—C8—H8A	108.9
O1—C1—N5	120.67 (11)	C9—C8—H8B	108.9
O1—C1—C2	121.75 (12)	C2—C8—H8B	108.9
N5—C1—C2	117.55 (10)	H8A—C8—H8B	107.7
C3—C2—C1	106.03 (10)	C10—C9—C8	176.60 (16)
C3—C2—C8	112.84 (10)	C9—C10—H10	180.0
C1—C2—C8	105.71 (10)	N3—C11—N2	110.81 (13)
C3—C2—C5	110.77 (10)	N3—C11—H11	124.6
C1—C2—C5	113.58 (10)	N2—C11—H11	124.6
C8—C2—C5	107.91 (10)	N4—C12—N2	111.01 (12)
N1—C3—C4	113.98 (12)	N4—C12—N5	125.45 (12)
N1—C3—C2	125.47 (11)	N2—C12—N5	123.34 (11)
C4—C3—C2	120.51 (11)	C14—C13—N5	110.59 (12)
C3—C4—H4A	109.5	C14—C13—H13A	109.5
C3—C4—H4B	109.5	N5—C13—H13A	109.5
H4A—C4—H4B	109.5	C14—C13—H13B	109.5
C3—C4—H4C	109.5	N5—C13—H13B	109.5
H4A—C4—H4C	109.5	H13A—C13—H13B	108.1
H4B—C4—H4C	109.5	C15—C14—C13	178.00 (18)
C6—C5—C2	113.64 (11)	C14—C15—H15	180.0
C6—C5—H5A	108.8

C3—N1—N2—C12	−40.63 (18)	C1—C2—C5—C6	37.77 (15)
C3—N1—N2—C11	151.13 (13)	C8—C2—C5—C6	−79.06 (13)
C11—N3—N4—C12	0.01 (16)	C3—C2—C8—C9	68.72 (15)
C12—N5—C1—O1	−174.64 (13)	C1—C2—C8—C9	−175.83 (11)
C13—N5—C1—O1	0.2 (2)	C5—C2—C8—C9	−53.99 (15)
C12—N5—C1—C2	3.4 (2)	C2—C8—C9—C10	72 (3)
C13—N5—C1—C2	178.27 (11)	N4—N3—C11—N2	−0.81 (16)
O1—C1—C2—C3	112.39 (14)	C12—N2—C11—N3	1.25 (15)
N5—C1—C2—C3	−65.67 (14)	N1—N2—C11—N3	172.10 (11)
O1—C1—C2—C8	−7.63 (17)	N3—N4—C12—N2	0.80 (15)
N5—C1—C2—C8	174.31 (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—C5	56.20 (15)	N1—N2—C12—N4	−171.23 (12)
N2—N1—C3—C4	173.10 (11)	C11—N2—C12—N5	173.80 (12)
N2—N1—C3—C2	−4.67 (18)	N1—N2—C12—N5	3.8 (2)
C1—C2—C3—N1	68.84 (15)	C1—N5—C12—N4	−148.84 (14)
C8—C2—C3—N1	−175.91 (12)	C13—N5—C12—N4	36.3 (2)
C5—C2—C3—N1	−54.80 (16)	C1—N5—C12—N2	36.8 (2)
C1—C2—C3—C4	−108.79 (13)	C13—N5—C12—N2	−138.05 (13)
C8—C2—C3—C4	6.46 (16)	C1—N5—C13—C14	−84.87 (17)
C5—C2—C3—C4	127.57 (13)	C12—N5—C13—C14	90.39 (15)
C3—C2—C5—C6	156.96 (11)

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃N₅O
M_r	279.30
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.6710 (2), 8.2415 (2), 12.9619 (3)
α, β, γ (°)	108.510 (1), 90.659 (1), 114.726 (1)
V (Å³)	695.85 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.3 × 0.3 × 0.3

Data collection
Diffractometer	Bruker APEX2 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	16879, 3187, 2577
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.129, 1.06
No. of reflections	3187
No. of parameters	191
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.26

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

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