4-({[6-(4-Chloro­benz­yl)-4-methyl-5-oxo-4,5-dihydro-1,2,4-triazin-3-yl]sulfan­yl}acetyl)-3-phenyl­sydnone

Hoong-Kun Fun; Madhukar Hemamalini; Nithinchandra; Balakrishna Kalluraya

doi:10.1107/S1600536811007689

. 2011 Mar 9;67(Pt 4):o820. doi: 10.1107/S1600536811007689

4-({[6-(4-Chlorobenzyl)-4-methyl-5-oxo-4,5-dihydro-1,2,4-triazin-3-yl]sulfanyl}acetyl)-3-phenylsydnone

Hoong-Kun Fun ^a,^*,^‡, Madhukar Hemamalini ^a, Nithinchandra ^b, Balakrishna Kalluraya ^b

PMCID: PMC3099780 PMID: 21754104

Abstract

In the title syndone (1,2,3-oxadiazol-3-ylium-5-olate) compound, C₂₁H₁₆ClN₅O₄S, the dihedral angle between the benzene and oxadiazole rings is 55.62 (11)° and that between the triazine and the chloro-substituted phenyl rings is 82.45 (9)°. There is an intramolecular C—H⋯S hydrogen bond, which generates an S(5) ring motif. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R ₂ ²(20) loops. The dimers are connected by C—H⋯N and C—H⋯O hydrogen bonds.

Related literature

For applications of sydnones, see: Rai et al. (2008 ▶); Jyothi et al. (2008 ▶).

Experimental

Crystal data

C₂₁H₁₆ClN₅O₄S
M _r = 469.90
Triclinic,
a = 6.4604 (1) Å
b = 10.1634 (2) Å
c = 16.9901 (4) Å
α = 105.264 (1)°
β = 92.103 (1)°
γ = 97.363 (1)°
V = 1064.44 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 296 K
0.62 × 0.39 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009) ▶ T _min = 0.828, T _max = 0.959
21841 measured reflections
6389 independent reflections
4781 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.154
S = 1.05
6389 reflections
290 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.49 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 datablocks global, I. DOI: 10.1107/S1600536811007689/hb5811sup1.cif

e-67-0o820-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007689/hb5811Isup2.hkl

e-67-0o820-Isup2.hkl^{(306.4KB, hkl)}

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
C7—H7B⋯O2ⁱ	0.97	2.52	3.429 (3)	157
C11—H11A⋯S1	0.96	2.12	2.7577 (17)	122
C11—H11B⋯N1ⁱⁱ	0.96	2.36	3.066 (2)	130
C11—H11B⋯N2ⁱⁱ	0.96	2.40	3.0304 (19)	123
C11—H11C⋯O1ⁱⁱⁱ	0.96	2.07	3.021 (2)	169

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

Acknowledgments

HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Sydnones (1,2,3-oxadiazol-3-ylium-5-olates) are mesoionic heterocyclic aromatic compounds. The study of sydnones still remains a field of interest because of their electronic structures and also because of the varied types of biological activities being reported (Rai et al., 2008). Recently sydnone derivatives were found to exhibit promising anti-microbial properties (Jyothi et al., 2008). Since their discovery, sydnones have shown diverse biological activities and it is thought that the meso-ionic nature of the sydnone ring promotes significant interactions with biological systems. Photochemical bromination of 3-aryl-4-acetylsydnone afforded 3-aryl-4 bromoacetylsydnones. Condensation of 6-(4-chlorobenzyl)-4-methyl-3- sulfanyl-1,2,4-triazin-5(4H)-one with 3-aryl-4-bromoacetylsydnones yielded S-substituted triazinone derivatives (Jyothi et al., 2008).

In the title compound (Fig. 1), the rings A (C16–C21), B (N4/N5/O4/C14–C15), C (N1/N2/N3/C8–C10) and D (C1–C6) are essentially planar. The dihedral angle between the best planes of the rings are A/B = 55.62 (11)°, A/C = 83.22 (10)°, A/D = 49.75 (11)°, B/C = 87.81 (9)°, B/D = 8.97 (10)° and C/D = 82.45 (9)°.

In the crystal (Fig. 2), symmetry-related molecules are linked into centrosymmetic dimers via pairs of intermolecular C—H···O hydrogen bonds, generating an R²₂(20) ring. Furthermore, these dimers are connected via C—H···N and C—H···O hydrogen bonds. There is an intramolecular C—H···S hydrogen bond, which generates an S(5) ring motif.

Experimental

To a mixture of 4-bromoacetyl-3-phenylsydnone (0.01 mol) and 6-(4-chlorobenzyl)-4-methyl-3-sulfanyl-1,2,4-triazin-5(4H)-one (0.01 mol) in ethanol, a catalytic amount of anhydrous sodium acetate was added. The solution was stirred at room temperature for 2-3hours. The solid product separated was filtered and dried. It was then recrystallized from ethanol. Colourless plates of (I) were obtained from 1:2 mixtures of DMF and ethanol by slow evaporation.