3-({4-[(2-Methyl­benzyl­idene)amino]-5-sulfanyl­idene-1H-1,2,4-triazol-3-yl}meth­yl)-1,3-benzoxazol-2(3H)-one

Abdullah Aydın; Nuray Hekimoğlu; Mehmet Akkurt; Tijen Önkol; Şölen Urlu Çiçekli; Orhan Büyükgüngör

doi:10.1107/S1600536812051458

. 2013 Jan 4;69(Pt 2):o169–o170. doi: 10.1107/S1600536812051458

3-({4-[(2-Methylbenzylidene)amino]-5-sulfanylidene-1H-1,2,4-triazol-3-yl}methyl)-1,3-benzoxazol-2(3H)-one

Abdullah Aydın ^a,^*, Nuray Hekimoğlu ^b, Mehmet Akkurt ^c, Tijen Önkol ^d, Şölen Urlu Çiçekli ^d, Orhan Büyükgüngör ^e

PMCID: PMC3569233 PMID: 23424456

Abstract

In the title compound, C₁₈H₁₅N₅O₂S, a weak intramolecular C—H⋯S hydrogen bond results in a small dihedral angle of 3.71 (9)° between the methylphenyl and triazole rings, which, in turn, form dihedral angles of 80.09 (8) and 77.32 (8)°, respectively, with the benzoxazolone mean plane. In the crystal, N—H⋯O hydrogen bonds link molecules into chains along [001], and weak C—H⋯N hydrogen bonds and π–π interactions between the five- and six-membered rings [centroid–centroid distances = 3.5074 (11) and 3.616 (1) Å] consolidate the crystal packing.

Related literature

For details of the synthesis, see: Urlu-Cicekli et al. (2012 ▶). For related structures, see: Aydın et al. (2005 ▶, 2012 ▶). For a MOPAC AM1 theoretical full-geometry optimization, see: Dewar et al. (1985 ▶); Stewart (1993 ▶). graphic file with name e-69-0o169-scheme1.jpg

Experimental

Crystal data

C₁₈H₁₅N₅O₂S
M _r = 365.42
Monoclinic,
a = 18.0823 (13) Å
b = 6.4623 (4) Å
c = 15.1892 (11) Å
β = 100.821 (6)°
V = 1743.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.62 × 0.48 × 0.22 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.881, T _max = 0.955
10084 measured reflections
3958 independent reflections
3034 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.110
S = 1.03
3958 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(27.1KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812051458/cv5375sup1.cif

e-69-0o169-sup1.cif^{(27.1KB, cif)}

Click here for additional data file.^{(194KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051458/cv5375Isup2.hkl

e-69-0o169-Isup2.hkl^{(194KB, hkl)}

Click here for additional data file.^{(6.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812051458/cv5375Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2ⁱ	0.86	2.03	2.856 (2)	162
C4—H4⋯N4ⁱⁱ	0.93	2.52	3.387 (3)	155
C11—H11⋯S1	0.93	2.48	3.2159 (18)	136

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

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant No. F.279 of the University Research Fund).

supplementary crystallographic information

Comment

In continuation of our studies of hybrid molecules containing 2(3H)- benzoxazolone fragment (Aydın et al., 2005), herewith we present the title compound, (I). In (I) (Fig. 1), the 2,3-dihydro-1,3-benzoxazole ring (N1/O1/C1—C7) is essentially planar with the maximum deviation of the C7 atom from the mean plane of -0.034 (2) Å. This ring system makes dihedral angles of 77.32 (8) and 80.09 (8)°, with the 4,5-dihydro-1H-1,2,4-triazole ring (N2–N4/C9/C10) and the benzene ring (C12–C17), respectively. The dihedral angle between the 4,5-dihydro-1H-1,2,4-triazole ring and the benzene ring is 3.71 (9)°. All bond lengths and angles are comparable with those observed in similar compounds (Aydın et al., 2005; 2012).

In the crystal, neighbouring molecules are linked by N—H···O and C—H···N hydrogen bonding interactions, forming a two dimensional network parallel to the (101) plane (Table 1, Fig. 2). In addition, the crystal packing is stabilized by a weak C—H···π interaction and two π-π stacking interactions [Cg1···Cg3(1 - x, -y, -z) = 3.5074 (11) Å and Cg2···Cg4(x, -1 + y,z) = 3.6160 (10) Å; where Cg1, Cg2, Cg3 and Cg4 are the centroids of the O1/C1/C6/N1/C7, N2/C9/N4/N3/C10, C1–C6 and C12–C17 rings, respectively].

Molecular orbital calculations using semi-empirical (AM1) have been carried out for the title compound with MOPAC (Dewar et al., 1985; Stewart, 1993). The values of the structural parameters of the title compound obtained by the results of the theoretical calculations (based on isolated molecules) and X-ray structural determinations in the solid state are almost identical within experimental error. The calculated dipole moment of (I) is 3.243 D. The HOMO and LUMO energy levels are -8.65563 and -.31527 eV, respectively.

Experimental

To a suspension of o-methylbenzaldehyde (0.0022 mol) in glacial acetic acid (3 ml), 0.002 mol [(4-amino-5-sulfanylidene-1,2,4-triazol-3-yl) methyl]-2(3H)-benzoxazolone was added. The reaction mixture was placed in microwave oven and irradiated for minutes changing between 15–30 min at 398 K (300 W). After completion of the reaction by monitoring with TLC, the reaction mixture was kept overnight at room temperature. The precipitate was collected by filtration, washed with water, dried, and crystallized from EtOH-acetone.

Yield, 58%, m.p.: 494–495 K. IR v_max cm^-1, 3186, 1772, 1484, 1268. ¹H-NMR (DMSO-d₆) δ 14.16 (1H, s, NH), 10.28 (1H, s, =CH), 7.84 (1H, d, Ar—H), 7.39 (1H, t, Ar—H), 7.29–7.18 (4H, m, Ar—H, H7, H4), 7.12 (1H, t, H6), 7.06 (1H, t, H5), 5.21 (2H, s, CH₂), 2.40 (3H, s, CH₃). Elemental analysis: C₁₈H₁₅N₅O₂S, Calc.(%) / Found (%): C:59.16/59.38, H: 4.14/3.95, N: 19.17/19.15. (Urlu-Cicekli et al., 2012).