4-[3-(Phen­oxy­meth­yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thia­diazin-6-yl]-3-(p-tol­yl)sydnone

Jia Hao Goh; Hoong-Kun Fun; Nithinchandra; B Kalluraya

doi:10.1107/S1600536810029910

. 2010 Jul 31;66(Pt 8):o2178–o2179. doi: 10.1107/S1600536810029910

4-[3-(Phenoxymethyl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazin-6-yl]-3-(p-tolyl)sydnone

Jia Hao Goh ^a,^‡, Hoong-Kun Fun ^a,^*,^§, Nithinchandra ^b, B Kalluraya ^b

PMCID: PMC3007409 PMID: 21588457

Abstract

In the title triazolothiadiazine derivative, C₂₀H₁₆N₆O₃S {systematic name: 3-(4-methylphenyl)-4-[3-(phenoxymethyl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazin-6-yl]-1,2,3-oxadiazol-3-ium-5-olate}, an S(6) ring motif is generated by an intramolecular C—H⋯O hydrogen bond. The 3,6-dihydro-1,3,4-thiadiazine ring adopts a twist-boat conformation. The dihedral angle between the 1,2,3-oxadiazole and 1,2,4-triazole rings is 46.45 (14)°. The 1,2,3-oxadiazole ring is inclined at dihedral angle of 59.49 (13)° with respect to the benzene ring attached to it. In the crystal structure, intermolecular C—H⋯O and C—H⋯N hydrogen bonds link neighbouring molecules into two-molecule-thick arrays parallel to the bc plane. A short S⋯O interaction [2.9565 (19) Å] also occurs.

Related literature

For general background to and applications of materials related to the title compound, see: Kalluraya & Rahiman (1997 ▶); Newton & Ramsden (1982 ▶); Wagner & Hill (1974 ▶). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ▶). For closely related structures, see: Goh et al. (2010a ▶,b ▶,c ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₀H₁₆N₆O₃S
M _r = 420.45
Monoclinic,
a = 20.6555 (7) Å
b = 8.1918 (3) Å
c = 11.1979 (4) Å
β = 96.127 (2)°
V = 1883.93 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.26 × 0.13 × 0.07 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.947, T _max = 0.985
17653 measured reflections
4318 independent reflections
2829 reflections with I > 2σ(I)
R _int = 0.065

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.133
S = 1.03
4318 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.53 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/S1600536810029910/hb5566sup1.cif

e-66-o2178-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029910/hb5566Isup2.hkl

e-66-o2178-Isup2.hkl^{(211.6KB, 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
C10—H10A⋯O3	0.97	2.26	3.026 (3)	135
C10—H10A⋯O3ⁱ	0.97	2.55	3.165 (3)	122
C10—H10B⋯O3ⁱⁱ	0.97	2.44	3.279 (3)	145
C19—H19A⋯N5ⁱⁱⁱ	0.93	2.61	3.491 (3)	158

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.

supplementary crystallographic information

Comment

Sydnones are a novel class of mesoionic compounds consisting of 1,2,3-oxadiazole ring system. A number of sydnone derivatives have shown diverse biological activities such as anti-inflammatory, analgesic and anti-arthritic (Newton & Ramsden, 1982; Wagner & Hill, 1974) properties. Sydnones possessing heterocyclic moieties at the 4-position are also known for a wide range of biological properties (Kalluraya & Rahiman, 1997). Encouraged by these reports and in continuation of our research for biologically active nitrogen containing heterocycles, a triazolothiadiazine moiety at the 4-position of the phenylsydnone was introduced.

In the title triazolothiadiazine derivative, an intramolecular C10—H10A···O3 hydrogen bond (Table 1) generates a six-membered ring, producing an S(6) hydrogen bond ring motif (Fig. 1, Bernstein et al., 1995). The 3,6-dihydro-1,3,4-thiadiazine ring (C9-C11/N3/N4/S1) adopts twist-boat conformation, with puckering parameters of Q = 0.634 (2) Å, θ = 67.08 (18)° and φ = 322.1 (2)° (Cremer & Pople, 1975). The dihedral angle formed between these essentially planar 1,2,3-oxadiazole (C12/C13/O2/N5/N6) and 1,2,4-triazole (C8/N1/N2/C9/N3) rings is 46.45 (14)°. The C1-C6 and C14-C19 phenyl rings are inclined at dihedral angles of 77.56 (14) and 59.49 (13)°, respectively, with respect to 1,2,3-oxadiazole and 1,2,4-triazole rings. The geometric parameters are consistent to those observed in closely related structures (Goh et al., 2010a,b,c).

In the crystal structure, intermolecular C10—H10A···O3, C10—H10B···O3 and C19—H19A···N5 hydrogen bonds (Table 1) interconnect neighbouring molecules into two-molecule-thick arrays parallel to the bc plane (Fig. 2). The interesting feature of the crystal structure is the intermolecular short S1···O3 interaction [2.9565 (19) Å; symmetry code: -x, -y, -z+1], which is significantly shorter than the sum of Van der Waals radii of the relevant atoms, further stabilizing the crystal structure.

Experimental

A solution of triazole (0.01 mol) and 4-bromoacetyl-3-tolylsydnone (0.01 mol) in absolute ethanol (20 ml) was heated under reflux for 10–12 h. The solution was concentrated, cooled to room temperature and neutrallized with 10 % sodium bicarbonate solution. The solid separated was filtered, washed with water, dried and recrystallized from ethanol. Colourless blocks of (I) were obtained from a 1:2 mixture of DMF and ethanol by slow evaporation.