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

Hoong-Kun Fun; Mohd Mustaqim Rosli; Nithinchandra; Balakrishna Kalluraya

doi:10.1107/S1600536811014504

. 2011 Apr 22;67(Pt 5):o1196. doi: 10.1107/S1600536811014504

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

Hoong-Kun Fun ^a,^*,^‡, Mohd Mustaqim Rosli ^a, Nithinchandra ^b, Balakrishna Kalluraya ^b

PMCID: PMC3089265 PMID: 21754498

Abstract

In the crystal, C₂₀H₁₅N₇O₆S, the dihedral angle between the oxadiazole and triazine rings is 86.94 (7)°. The oxadiazole ring makes a dihedral angle of 52.96 (8)° with the phenyl ring, while the triazine ring makes a dihedral angle of 82.08 (7)° with the benzene ring. In the structure, molecules are linked by a pair of N—H⋯O hydrogen bonds, forming an inversion dimer. The dimers are further stacked along the a axis via N—H⋯N hydrogen bonds. Weak intermolecular C—H⋯O interactions are also observed.

Related literature

For the biological activity of sydnone derivatives, see: Rai et al. (2008 ▶); Jyothi et al. (2008 ▶); Kalluraya et al. (2008a ▶,b ▶). For a related structure, see: Fun et al. (2011 ▶).

Experimental

Crystal data

C₂₀H₁₅N₇O₆S
M _r = 481.45
Triclinic,
a = 6.4071 (1) Å
b = 10.1629 (2) Å
c = 17.1521 (3) Å
α = 106.372 (1)°
β = 92.400 (1)°
γ = 97.551 (1)°
V = 1058.61 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 297 K
0.51 × 0.34 × 0.17 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.900, T _max = 0.965
21821 measured reflections
7793 independent reflections
5330 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.131
S = 1.04
7793 reflections
315 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 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/S1600536811014504/is2702sup1.cif

e-67-o1196-sup1.cif^{(22.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014504/is2702Isup2.hkl

e-67-o1196-Isup2.hkl^{(381.2KB, 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
N7—H2N7⋯O4ⁱ	0.89 (2)	2.15 (2)	3.0152 (19)	163.5 (18)
N7—H1N7⋯N4ⁱⁱ	0.89 (2)	2.43 (2)	3.1019 (17)	133.1 (17)
N7—H1N7⋯N5ⁱⁱ	0.89 (2)	2.45 (2)	3.0166 (16)	122.5 (16)
C3—H3A⋯O5ⁱⁱⁱ	0.93	2.57	3.345 (3)	141
C14—H14A⋯O3^iv	0.97	2.53	3.4443 (18)	157

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

Acknowledgments

HKF and MMR thank USM for the Research University Grant (No. 1001/PFIZIK/811160).

supplementary crystallographic information

Comment

Sydnones 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 displayed by some of them (Rai et al., 2008). Recently sydnone derivatives were found to exhibit promising antimicrobial properties (Kalluraya 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. Because of wide variety of properties displayed by sydnones ,we were prompted to synthesize a new S-substituted triazinones containing a sydnone ring.

Photochemical bromination of 3-aryl-4-acetylsydnone afforded 3-aryl-4 bromoacetylsydnones. Condensation of 4-amino-6-(p-nitrobenzyl)-3-sulfanyl-1,2,4-triazin-5(4H)-one with 3-phenyl-4-bromoacetylsydnones yielded S-substituted triazinone derivatives (Jyothi et al., 2008).

All parameters in (I), Fig. 1, are within normal ranges and comparable with the related structure (Fun et al., 2011). The dihedral angle between oxadiazole (C7/C8/N1/N2/O1) and triazine (C11/N3/C12/C13/N4/N5) groups is 86.94 (7)°. The oxadiazole and triazine groups make dihedral angles of 52.96 (8) and 83.08 (7)° with the C1–C6 phneyl ring and 9.51 (8) and 82.08 (7)° with the C15–C20 benzene ring, respectively.

In the crystal structure, the N7—H2N7···O4ⁱ, N7—H1N7···N4ⁱⁱ, N7—H1N7···N5ⁱⁱ, C3—H3A···O5ⁱⁱⁱ and C14—H14A···O3^iv intermolecular interactions (Table 1) link the molecules into two-dimensional sheets parallel to the ac-plane (Fig. 2).

Experimental

To a solution of 4-bromoacetyl-3-phenylsydnone (0.01mol) and 4-amino-6-(p-nitrobenzyl)-3-sulfanyl-1,2,4-triazin-5(4H)-one (0.01mol) in ethanol, a catalytic amount of anhydrous sodium acetate was added. The solution was stirred at room temperature for 2-3 hours. 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 1:2 mixtures of DMF and ethanol by slow evaporation.