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

El Bakri, Y.; Harmaoui, A.; Essassi, E.M.; Saadi, M.; El Ammari, L.

doi:10.1107/S2414314616012293

organic compounds

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Volume 1| Part 8| August 2016| x161229

doi:10.1107/S2414314616012293

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

Youness El Bakri,^a ^* Abdallah Harmaoui,^a El Mokhtar Essassi,^a Mohamed Saadi ^b and Lahcen El Ammari ^b

^aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétences Pharmacochimie, Mohammed V University in Rabat, BP 1014 Avenue Ibn Batouta, Rabat, Morocco, and ^bLaboratoire de Chimie du Solide Appliquée, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: y_elbakri@yahoo.com

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 20 July 2016; accepted 29 July 2016; online 2 August 2016)

In the molecule of the title compound, C₆H₇N₅S, the triazole ring is planar, while the triazepine ring displays a boat conformation. The dihedral angle between the mean plane through the triazole and triazepine rings is 18.48 (8)°. In the crystal, molecules are linked into centrosymmetric dimers by N—H⋯N hydrogen bonds via eight-membered {⋯HNCN}₂ synthons. Supramolecular layers in the ab plane are sustained by C—H⋯N and π–π interactions [inter-centroid separation between triazole rings = 3.2880 (16) Å]. Connections along the c axis occur between S atoms [S⋯S = 3.5972 (16) Å].

Keywords: crystal structure; triazole; triazepin-8(9H)-thione; hydrogen bonds.

CCDC reference: 1496665

Structure description

Triazolotriazepine derivatives have been used as potent inhibitors of bone resorption (Chikazu et al., 2000 ). They also exhibit anti-fungal activity (Gupta et al., 2011 ). In view of the potential biological activity of fused azepines (Dabholkar & More, 2004 ; Sewell & Hawking, 1950 ; Acheson & Taylor, 1956 ) and as part of our interest in the synthesis of new heterocyclic systems containing triazole rings and triazepine (Essassi et al., 1976 , 1977 ; Gupta, 2007 ), the title compound was synthesized and its crystal structure determined.

The molecule of the title compound is built up from two fused rings linked to a methyl group and a thione-sulfur atom as shown in Fig. 1. The mean plane through the triazepine ring makes a dihedral angle of 18.48 (8)° with the triazole ring. The triazepine ring adopts a boat conformation as indicated by the total puckering amplitude Q_T = 0.7882 (15) Å and spherical polar angles θ2 = 71.71 (10)° with φ2 = 22.27 (11)° and φ3 = 122.3 (3)° (calculated using PARST; Nardelli, 1983 ).

Figure 1
Plot of the molecule of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

In the crystal, the molecules are linked into supramolecular layers in the ab plane by N5—H5N⋯N4, C2—H2A⋯N3 and C5—H5⋯N1 hydrogen bonds, Table 1, in addition to π–π interactions between triazole rings, Fig. 2. Connections along the c axis occur between sulfur atoms [S⋯S = 3.5972 (16) Å]

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5N⋯N4ⁱ	0.86	2.01	2.8530 (18)	167
C2—H2A⋯N3ⁱⁱ	0.97	2.56	3.487 (2)	161
C5—H5⋯N1ⁱⁱⁱ	0.93	2.58	3.442 (2)	155
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y, -z+1; (iii) -x, -y+1, -z+1.

Figure 2
Plot showing molecules linked by N—H⋯N and C–H⋯N hydrogen bonds, in addition to π–π interactions.

Synthesis and crystallization

To a solution of 6-methyl-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazepin-8(9H)-one (2 g, 12 mmol) and phosphore pentasulfide (2.7 g, 15 mmol) was added a small amount of sodium bicarbonate. The reaction mixture was heated at gentle reflux for 4 h then evaporated to dryness. The residue was taken up in boiling water (20 ml) and the precipitate that formed by cooling was filtered. The purified product was crystallized from ethanol to give colourless crystals in a yield of 65%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₇N₅S
M_r	181.23
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	6.238 (2), 7.234 (3), 10.887 (4)
α, β, γ (°)	103.331 (15), 92.329 (16), 113.846 (15)
V (Å³)	432.3 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.33
Crystal size (mm)	0.35 × 0.30 × 0.26

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.644, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	10195, 2287, 2038
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.694

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.119, 1.07
No. of reflections	2287
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.38
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1496665

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616012293/tk4020sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616012293/tk4020Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616012293/tk4020Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).

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

Crystal data top

C₆H₇N₅S	Z = 2
M_r = 181.23	F(000) = 188
Triclinic, P1	D_x = 1.392 Mg m⁻³
a = 6.238 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.234 (3) Å	Cell parameters from 2287 reflections
c = 10.887 (4) Å	θ = 3.2–29.6°
α = 103.331 (15)°	µ = 0.33 mm⁻¹
β = 92.329 (16)°	T = 296 K
γ = 113.846 (15)°	Block, colourless
V = 432.3 (3) Å³	0.35 × 0.30 × 0.26 mm

Data collection top

Bruker X8 APEX diffractometer	2287 independent reflections
Radiation source: fine-focus sealed tube	2038 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
φ and ω scans	θ_max = 29.6°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→8
T_min = 0.644, T_max = 0.747	k = −10→10
10195 measured reflections	l = −14→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0613P)² + 0.1769P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2287 reflections	Δρ_max = 0.47 e Å⁻³
110 parameters	Δρ_min = −0.38 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
C1	0.5444 (3)	0.3425 (2)	0.76025 (13)	0.0284 (3)
C2	0.3456 (3)	0.4034 (2)	0.79409 (13)	0.0306 (3)
H2A	0.1951	0.2807	0.7656	0.037*
H2B	0.3627	0.4553	0.8861	0.037*
C3	0.3466 (3)	0.5699 (2)	0.73291 (14)	0.0318 (3)
C4	0.4105 (4)	0.7857 (3)	0.81648 (19)	0.0507 (5)
H4A	0.5692	0.8425	0.8607	0.076*
H4B	0.3025	0.7790	0.8775	0.076*
H4C	0.4007	0.8741	0.7650	0.076*
C5	0.1097 (3)	0.2566 (2)	0.41943 (15)	0.0344 (3)
H5	0.0219	0.3170	0.3869	0.041*
C6	0.3465 (2)	0.2043 (2)	0.54244 (13)	0.0253 (3)
N1	0.2954 (2)	0.54000 (18)	0.61292 (13)	0.0324 (3)
N2	0.2479 (2)	0.33992 (17)	0.53619 (11)	0.0275 (2)
N3	0.1165 (2)	0.0823 (2)	0.35948 (12)	0.0345 (3)
N4	0.2688 (2)	0.04725 (18)	0.43825 (11)	0.0295 (3)
N5	0.5193 (2)	0.23657 (19)	0.63695 (11)	0.0290 (3)
H5N	0.6036	0.1688	0.6148	0.035*
S1	0.77311 (8)	0.39546 (8)	0.86328 (4)	0.04839 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0301 (7)	0.0290 (6)	0.0273 (6)	0.0153 (5)	0.0046 (5)	0.0045 (5)
C2	0.0326 (7)	0.0352 (7)	0.0271 (6)	0.0192 (6)	0.0079 (5)	0.0045 (5)
C3	0.0310 (7)	0.0285 (6)	0.0360 (7)	0.0160 (5)	0.0074 (6)	0.0020 (5)
C4	0.0658 (12)	0.0320 (8)	0.0477 (10)	0.0219 (8)	0.0097 (9)	−0.0037 (7)
C5	0.0345 (7)	0.0372 (7)	0.0336 (7)	0.0197 (6)	−0.0010 (6)	0.0059 (6)
C6	0.0259 (6)	0.0253 (6)	0.0271 (6)	0.0140 (5)	0.0056 (5)	0.0051 (5)
N1	0.0369 (6)	0.0246 (5)	0.0380 (7)	0.0176 (5)	0.0062 (5)	0.0042 (4)
N2	0.0292 (6)	0.0257 (5)	0.0294 (6)	0.0155 (4)	0.0027 (4)	0.0041 (4)
N3	0.0334 (6)	0.0378 (6)	0.0308 (6)	0.0178 (5)	−0.0017 (5)	0.0024 (5)
N4	0.0314 (6)	0.0287 (5)	0.0280 (6)	0.0158 (5)	0.0022 (4)	0.0017 (4)
N5	0.0317 (6)	0.0332 (6)	0.0261 (5)	0.0212 (5)	0.0029 (4)	0.0015 (4)
S1	0.0423 (3)	0.0695 (3)	0.0326 (2)	0.0328 (2)	−0.00534 (17)	−0.00263 (19)

Geometric parameters (Å, º) top

C1—N5	1.3509 (18)	C4—H4C	0.9600
C1—C2	1.5072 (19)	C5—N3	1.298 (2)
C1—S1	1.6343 (16)	C5—N2	1.3636 (19)
C2—C3	1.503 (2)	C5—H5	0.9300
C2—H2A	0.9700	C6—N4	1.3144 (17)
C2—H2B	0.9700	C6—N2	1.3647 (17)
C3—N1	1.279 (2)	C6—N5	1.3675 (18)
C3—C4	1.495 (2)	N1—N2	1.3986 (16)
C4—H4A	0.9600	N3—N4	1.3898 (18)
C4—H4B	0.9600	N5—H5N	0.8599

N5—C1—C2	114.93 (12)	H4B—C4—H4C	109.5
N5—C1—S1	121.53 (11)	N3—C5—N2	111.33 (13)
C2—C1—S1	123.54 (10)	N3—C5—H5	124.3
C3—C2—C1	111.00 (12)	N2—C5—H5	124.3
C3—C2—H2A	109.4	N4—C6—N2	110.24 (12)
C1—C2—H2A	109.4	N4—C6—N5	124.33 (12)
C3—C2—H2B	109.4	N2—C6—N5	125.12 (12)
C1—C2—H2B	109.4	C3—N1—N2	115.92 (12)
H2A—C2—H2B	108.0	C5—N2—C6	104.35 (11)
N1—C3—C4	117.00 (15)	C5—N2—N1	122.64 (12)
N1—C3—C2	124.37 (12)	C6—N2—N1	132.08 (12)
C4—C3—C2	118.62 (15)	C5—N3—N4	106.88 (12)
C3—C4—H4A	109.5	C6—N4—N3	107.19 (12)
C3—C4—H4B	109.5	C1—N5—C6	125.05 (12)
H4A—C4—H4B	109.5	C1—N5—H5N	120.1
C3—C4—H4C	109.5	C6—N5—H5N	114.4
H4A—C4—H4C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5N···N4ⁱ	0.86	2.01	2.8530 (18)	167
C2—H2A···N3ⁱⁱ	0.97	2.56	3.487 (2)	161
C5—H5···N1ⁱⁱⁱ	0.93	2.58	3.442 (2)	155

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z+1; (iii) −x, −y+1, −z+1.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements and the University Sultan Moulay Slimane, Beni-Mellal, Morocco, for financial support.

References

Acheson, R. M. & Taylor, N. F. (1956). J. Chem. Soc. pp. 4727–4731. CrossRef Web of Science Google Scholar
Bruker (2009). APEX2 and SAINT . Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Chikazu, D., Shindo, M., Iwasaka, T., Katagiri, M., Manabe, N., Takato, T., Nakamura, K. & Kawaguchi, H. (2000). J. Bone Miner. Res. 15, 674–682. Web of Science CrossRef PubMed CAS Google Scholar
Dabholkar, V. V. & More, G. D. (2004). Indian J. Chem. Sect. B, 43, 682–684. Google Scholar
Essassi, E. M., Lavergne, J. P. & Viallefont, P. (1976). J. Heterocycl. Chem. 13, 885–887. CrossRef CAS Google Scholar
Essassi, E. M., Lavergne, J. P. & Viallffont, P. (1977). Tetrahedron, 33, 2807–2812. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gupta, M. (2007). J. Heterocycl. Chem. 44, 1023–1027. CrossRef CAS Google Scholar
Gupta, M., Paul, S. & Gupta, R. (2011). Eur. J. Med. Chem. 46, 631–635. Web of Science CrossRef CAS PubMed Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sewell, P. & Hawking, F. (1950). Brit. J. Pharmacol. 5, 239–260. PubMed CAS Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161229

doi:10.1107/S2414314616012293

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds