3-Phenyl-4-{3-[(p-tol­yloxy)meth­yl]-7H-1,2,4-triazolo[3,4-b][1,3,4]thia­diazin-6-yl}sydnone

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

doi:10.1107/S160053681002982X

. 2010 Jul 31;66(Pt 8):o2162–o2163. doi: 10.1107/S160053681002982X

3-Phenyl-4-{3-[(p-tolyloxy)methyl]-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazin-6-yl}sydnone

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

PMCID: PMC3007576 PMID: 21588446

Abstract

In the title compound (systematic name: 3-phenyl-4-{3-[(p-tolyloxy)methyl]-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazin-6-yl}-1,2,3-oxadiazol-3-ium-5-olate), C₂₀H₁₆N₆O₃S, an intramolecular C—H⋯O hydrogen bond generates an S(6) ring motif. The 3,6-dihydro-1,3,4-thiadiazine ring adopts a twist-boat conformation. The 1,2,3-oxadiazole and 1,2,4-triazole rings are inclined to each other at an interplanar angle of 44.13 (13)°. The phenyl ring makes an interplanar angle of 67.40 (13)° with the attached 1,2,3-oxadiazole ring. In the crystal structure, adjacent molecules are interconnected into two-molecule-thick arrays parallel to (100) via C—H⋯O and C—H⋯N hydrogen bonds. A short S⋯O contact [2.9512 (18) Å] is observed.

Related literature

For general background to, and applications of materials related to the title compound, see: Hedge et al. (2008 ▶), Kalluraya & Rahiman (1997 ▶); Kalluraya et al. (2003 ▶). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ▶). For 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 = 42.0781 (12) Å
b = 8.2304 (2) Å
c = 11.1488 (3) Å
β = 101.630 (2)°
V = 3781.78 (17) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.29 × 0.13 × 0.05 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.942, T _max = 0.989
11383 measured reflections
3486 independent reflections
2496 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.101
S = 1.03
3486 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.40 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/S160053681002982X/hb5565sup1.cif

e-66-o2162-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002982X/hb5565Isup2.hkl

e-66-o2162-Isup2.hkl^{(171.1KB, 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	2.27	3.041 (3)	135
C10—H10A⋯O3ⁱ	0.97	2.54	3.162 (3)	122
C10—H10B⋯O3ⁱⁱ	0.97	2.46	3.292 (3)	144
C19—H19A⋯N5ⁱⁱⁱ	0.93	2.57	3.386 (3)	147

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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

Triazolothiadiazines have shown to possess significant biological and pharmacological activities such as anthelmintic, analgesic and anti-inflammatory (Kalluraya & Rahiman, 1997) properties. Encouraged by these literatures, we have synthesized triazolothiadiazines containing the sydnone moiety. The introduction of sydnone moiety into an heterocyclic compound will increase the biological and pharmacological activities of heterocyclic system (Hedge et al., 2008). Triazolothiadiazines were synthesized by the condensation of 4-bromoacetyl-3-arylsydnones with 3-aryloxymethyl-4-amino-5-mercapto-1,2,4-triazoles. 4-Bromoacetyl-3-arylsydnones were in turn obtained by the photochemical bromination of 4-acetyl-3-arylsydnones (Kalluraya et al., 2003).

In the title compound, (I), 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 = 0.630 (2) Å, θ = 67.03 (18)° and φ = 323.0 (2)° (Cremer & Pople, 1975). The essentially planar 1,2,3-oxadiazole (C12/C13/O2/N5/N6) and 1,2,4-triazole (C8/N1/N2/C9/N3) rings are inclined to each other at interplanar angle of 44.13 (13)°. The C14-C19 phenyl ring is inclined at interplanar angle of 67.40 (13)° with respect to the attached 1,2,3-oxadiazole ring. The geometric parameters are comparable to those reported 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) link adjacent molecules into two-molecule-thick arrays parallel to (100) plane (Fig. 2). Interestingly, further stabilization of the crystal structure is provided by intermolecular short S1···O3 interaction [2.9512 (18) Å; symmetry code: -x+1/2, -y+1/2, -z] which is significantly shorter than the sum of Van der Waals radii of the relevant atoms.

Experimental

A solution of triazole (0.01 mol) and 4-bromoacetyl-3-phenylsydnone (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 separated solid 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.