Crystal structure of 6,9-dimethyl-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazepin-8(9H)-one 0.40-hydrate

Abdellah Harmaoui; Rachid Bouhfid; El Mokhtar Essassi; Mohamed Saadi; Lahcen El Ammari

doi:10.1107/S2056989014025687

. 2015 Jan 1;71(Pt 1):o1–o2. doi: 10.1107/S2056989014025687

Crystal structure of 6,9-dimethyl-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazepin-8(9H)-one 0.40-hydrate

Abdellah Harmaoui ^a,^*, Rachid Bouhfid ^b, El Mokhtar Essassi ^a,^b, Mohamed Saadi ^c, Lahcen El Ammari ^c

PMCID: PMC4331897 PMID: 25705477

Abstract

In the molecule of the title compound, C₇H₉N₅O·0.40H₂O, the seven-membered heterocyclic ring exhibits a boat conformation, whereas the five-membered triazole ring is almost planar (r.m.s. deviation = 0.005 Å). In the crystal, centrosymmetric dimers are linked by pairs of C—H⋯O hydrogen bonds into dimers, which are further connected via O—H⋯N and C—H⋯N hydrogen bonds, forming a three-dimensional network. The structure contains a partially occupied water molecule lying on a twofold axis with an occupancy factor of 0.4.

Keywords: crystal structure; 1,2,4-triazepin-8(9H)-one; pharmacological and biological activities; hydrogen bonding

Related literature

For pharmacological and biological activities of 1,2,4-triazole and 1,2,4-triazepine derivatives, see: Gupta et al. (2011 ▸); Mathew et al. (2006 ▸); Reed et al. (2010 ▸). For related structures, see: Essassi et al. (1977 ▸); Doubia et al. (2007 ▸); Zemama et al. (2009 ▸). graphic file with name e-71-000o1-scheme1.jpg

Experimental

Crystal data

C₇H₉N₅O·0.4H₂O
M _r = 186.44
Monoclinic,
a = 11.4970 (18) Å
b = 11.4527 (18) Å
c = 14.867 (2) Å
β = 109.615 (4)°
V = 1843.9 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.40 × 0.34 × 0.30 mm

Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T _min = 0.637, T _max = 0.746
14175 measured reflections
2039 independent reflections
1600 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.125
S = 1.04
2039 reflections
123 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: SAINT-Plus (Bruker, 2009 ▸); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸) and publCIF (Westrip,2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989014025687/rz5141sup1.cif

e-71-000o1-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014025687/rz5141Isup2.hkl

e-71-000o1-Isup2.hkl^{(100.4KB, hkl)}

Click here for additional data file.^{(4.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014025687/rz5141Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989014025687/rz5141fig1.tif

The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level, showing the intermolecular O—H⋯N hydrogen bond (dashed line).

Click here for additional data file.^{(1.6MB, tif)}

. DOI: 10.1107/S2056989014025687/rz5141fig2.tif

Partiel crystal packing of the title compound, showing molecules linked through C—H⋯O and O—H⋯N hydrogen bonds (dashed lines).

CCDC reference: 1035668

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C2H2AN3ⁱ	0.97	2.58	3.449(3)	149
C5H5O1ⁱⁱ	0.93	2.29	3.211(2)	173
O2H1N3ⁱⁱⁱ	0.87	2.08	2.939(2)	167

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.

supplementary crystallographic information

S1. Comment

1,2,4-Triazole derivatives are known to possess wide biological significance and diverse pharmacological activities (Mathew et al., 2006; Reed et al., 2010). 1,2,4-Triazepine derivatives were also reported to possess antibacterial, antiviral and psychotropic activities (Gupta et al., 2011). They are also the reactants for the synthesis of other heterocyclic compounds (Essassi et al., 1977; Doubia et al., 2007; Zemama et al., 2009). The aim of the present paper is to report the crystal structure of the title compound.

The molecule of the title compound is build up from two fused five- and seven-membered rings linked to two methyl groups and crystallizing with a partial water molecule as shown in Fig. 1. The triazepine ring adopts a boat conformation as indicated by the puckering amplitude Q = 0.7865 (17) Å and spherical polar angle θ = 88.80 (12)°, with φ = 60.07 (13)°. The triazole ring is close to be planar, with a maximum deviation of 0.007 (2) Å for atom C5. In the crystal, centrosymmetrically-related molecules are linked by pairs of weak C—H···O hydrogen bonds into dimeric units, which are further connected into a three-dimensional network by O—H···N and C—H···O hydrogen bonds (Fig. 2, Table 1).

S2. Experimental

To a solution of 1 g (0,06 mol) of6-methyl-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazepin-8(9H)-one in 30 ml of sodium methoxide (prepared from 30 ml of methanol and 0.15 g of sodium) was added 1 g (0.007 mol) of methyl iodide and the mixture was heated for 5 h. The solution was then concentrated to dryness under reduced pressure and the residue was extracted with chloroform. The precipitate obtained was chromatographed on a silica column (eluent: chloroform/ethanol 95:5 v/v). The purified product was crystallized from ethanol to give colourless crystals with a yield of 50%.