(E)-4-{[(3-Propyl-5-sulfanyl­idene-4,5-dihydro-1H-1,2,4-triazol-4-yl)imino]­meth­yl}-3-(p-tol­yl)-1,2,3-oxadiazol-3-ium-5-olate

Hoong-Kun Fun; Ching Kheng Quah; Nithinchandra; Balakrishna Kalluraya

doi:10.1107/S1600536811037287

. 2011 Sep 17;67(Pt 10):o2668–o2669. doi: 10.1107/S1600536811037287

(E)-4-{[(3-Propyl-5-sulfanylidene-4,5-dihydro-1H-1,2,4-triazol-4-yl)imino]methyl}-3-(p-tolyl)-1,2,3-oxadiazol-3-ium-5-olate

Hoong-Kun Fun ^a,^*,^‡, Ching Kheng Quah ^a,^§, Nithinchandra ^b, Balakrishna Kalluraya ^b

PMCID: PMC3201362 PMID: 22065521

Abstract

The title compound, C₁₅H₁₆N₆O₂S, exists in a trans configuration with respect to the acyclic N=C bond. The 1,2,3-oxadiazol-3-ium ring makes dihedral angles of 10.59 (8) and 73.94 (8)°, respectively, with the 1,2,4-triazole and benzene rings. The molecular structure is stabilized by an intramolecular C—H⋯S hydrogen bond, which generates an S(6) ring motif. In the crystal, molecules are linked into inversion dimers by pairs of intermolecular N—H⋯S hydrogen bonds, generating eight-membered R ₂ ²(8) ring motifs. The dimers are further connected by C—H⋯O hydrogen bonds, forming a sheet parallel to the bc plane. The ethyl group is disordered over two sets of sites with occupancies of 0.744 (7) and 0.256 (7).

Related literature

For general background to and applications of sydnone derivatives, see: Baker et al. (1949 ▶); Hedge et al. (2008 ▶); Rai et al. (2008 ▶); Kalluraya et al. (2002 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). For a related structure, see: Fun et al. (2011 ▶).

Experimental

Crystal data

C₁₅H₁₆N₆O₂S
M _r = 344.40
Monoclinic,
a = 13.4220 (11) Å
b = 6.2411 (5) Å
c = 21.1374 (16) Å
β = 104.575 (2)°
V = 1713.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.51 × 0.17 × 0.08 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.865, T _max = 0.983
18912 measured reflections
5003 independent reflections
3637 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.123
S = 1.04
5003 reflections
243 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037287/is2776sup1.cif

e-67-o2668-sup1.cif^{(21.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037287/is2776Isup2.hkl

e-67-o2668-Isup2.hkl^{(245KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811037287/is2776Isup3.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
N5—H1N5⋯S1ⁱ	0.857 (18)	2.440 (18)	3.2933 (13)	174.3 (16)
C1—H1A⋯O2ⁱⁱ	0.93	2.48	3.346 (2)	154
C9—H9A⋯S1	0.93	2.42	3.1845 (13)	139

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

Acknowledgments

HKF and CKQ thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160).

supplementary crystallographic information

Comment

Sydnones constitute a well defined class of mesoionic compounds consisting of 1,2,3-oxadiazole ring system. The introduction of the concept of mesoionic structure for certain heterocyclic compounds in the year 1949

has proved to be a fruitful development in heterocyclic chemistry (Baker et al., 1949). The study of sydnones still remains a field of interest because of their electronic structures and also because of the various types of biological activities displayed by some of them. Interest in sydnone derivatives has also been encouraged by the discovery that they exhibit various pharmacological activities (Hedge et al., 2008; Rai et al., 2008). The 4-formyl sydnone will be used for the preparation of a new series of Schiff bases by condensation with appropriate 4-amino-4H-1,2,4-triazole-3-thiol. These Schiff bases containing sydnone is utilized for the synthesis of appropriate Mannich bases (Kalluraya et al., 2002).

The molecular structure is shown in Fig. 1. Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to a related structure (Fun et al., 2011). The title compound exists in trans configuration with respect to the acyclic N3═C9 bond [bond lengths = 1.2669 (17) Å]. The 1,2,4-triazole (N4–N6/C10/C11, maximum deviation of 0.004 (1) Å at atom N4) and the phenyl (C1–C6) rings form dihedral angles of 73.94 (8) and 10.59 (8)°, respectively, with the 1,2,3-oxadiazol-3-ium ring (O1/N1/N2/C7/C8, maximum deviation of 0.004 (1) Å at atoms C7 and C8). The molecular structure is stabilized by an intramolecular C9–H9A···S1 hydrogen bond, which generates an S(6) ring motif (Fig. 1, Bernstein et al., 1995). The ethyl group is disordered over two sets of sites in a 0.744 (7): 0.256 (7) ratio.

In the crystal (Fig. 2), the intermolecular N5—H1N5···S1 hydrogen bonds (Table 1) form the inversion dimers and produce eight-membered ring motifs R²₂(8) (Bernstein et al., 1995). Another intermolecular C1—H1A···O2 hydrogen bond connects these dimers to another molecule forming two-dimensional sheets parallel to the bc plane.

Experimental

4-Formyl-3-p-tolylsydnone (0.01 mol) and 4-amino-5-propyl-4H-1,2,4-triazole-3-thiol (0.01 mol) in ethanol and a catalytic amount of conc. sulphuric acid was stirred at room temperature for 2-3 h. The solid product that separated out was filtered and dried. It was then recrystallized from ethanol. Crystals suitable for X-ray analysis were obtained from a 1:2 mixture solution of DMF and ethanol by slow evaporation.