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

Abstract

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,

• a = 7.4674 (3) Å

• b = 8.3398 (3) Å

• c = 20.2214 (6) Å

• β = 95.174 (2)°

• V = 1254.19 (8) ų

• 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[F ² > 2σ(F ²)] = 0.053

• wR(F ²) = 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Experimental

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

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).

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of C12H15N5O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C12H15N5O	F(000) = 520
Mr = 245.29	Dx = 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

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

Refinement

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(Fo2) + (0.1011P)2 + 0.1814P] where P = (Fo2 + 2Fc2)/3
2435 reflections	(Δ/σ)max = 0.001
164 parameters	Δρmax = 0.62 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)