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

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

doi:10.1107/S1600536811010786

. 2011 Mar 31;67(Pt 4):o1005–o1006. doi: 10.1107/S1600536811010786

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

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

PMCID: PMC3099773 PMID: 21754026

Abstract

In the title compound, C₂₀H₁₇N₇O₂S (systematic name: 3-(4-methylphenyl)-4-{3-[(phenylamino)methyl]-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazin-6-yl}-1,2,3-oxadiazol-3-ium-5-olate), the 3,6-dihydro-2H-1,3,4-thiadiazine ring adopts a half-boat conformation. The oxadiazol-3-ium ring makes dihedral angles of 57.99 (6) and 54.48 (6)° with the phenyl and benzene rings, respectively, while the 1,2,4-triazole ring forms corresponding angles of 37.35 (6) and 73.89 (6)°. The dihedral angle between the oxadiazol-3-ium and 1,2,4-triazole rings is 21.12 (6)°. In the crystal, the molecules are linked via intermolecular N—H⋯O and C—H⋯N hydrogen bonds into a layer parallel to the (100) plane. The crystal structure is further consolidated by C—H⋯π interactions. An intramolecular C—H⋯O hydrogen bond is also observed, which generates an S(6) ring motif.

Related literature

For general background to and the biological activity of sydnone derivatives, see: Rai et al. (2008 ▶); Kalluraya et al. (2002 ▶); Hedge et al. (2008 ▶). For general background to and the biological activity of triazolothiadiazine derivatives, see: Kalluraya & Rahiman (1997 ▶). For the synthesis of triazolothiadiazines, see: Kalluraya et al. (2003 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₀H₁₇N₇O₂S
M _r = 419.47
Monoclinic,
a = 10.1210 (4) Å
b = 10.5065 (4) Å
c = 19.6370 (6) Å
β = 114.550 (2)°
V = 1899.36 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.35 × 0.28 × 0.27 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.932, T _max = 0.947
22363 measured reflections
6845 independent reflections
5754 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.109
S = 1.06
6845 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.25 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/S1600536811010786/is2692sup1.cif

e-67-o1005-sup1.cif^{(22.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010786/is2692Isup2.hkl

e-67-o1005-Isup2.hkl^{(335KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O2	0.97	2.40	3.1654 (14)	136
N1—H1⋯O2ⁱ	0.86	2.20	3.0218 (11)	160
C18—H18A⋯N2ⁱⁱ	0.93	2.62	3.4246 (14)	145
C15—H15A⋯Cg1ⁱⁱⁱ	0.93	2.73	3.5537 (14)	148

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

Acknowledgments

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

supplementary crystallographic information

Comment

Sydnones are mesoionic heterocyclic aromatic compounds. The study of sydnones remains as a field of interest because of their electronic structures and 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., 2002). Triazolothiadiazines 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).

The bond lengths (Allen et al., 1987) and angles in the molecule (Fig. 1) are within normal ranges. The molecular structure is stabilized by an intramolecular C10–H10A···O2 hydrogen bond which generates an S(6) ring motif (Bernstein et al., 1995). The 3,6-dihydro-2H-1,3,4-thiadiazine ring (S1/N5/N6/C9–C11) adopts a half-boat conformation with atom C10 deviating by 0.340 (1) Å from the mean plane through the remaining atoms, puckering parameters (Cremer & Pople, 1975) Q = 0.5312 (9) Å, Θ = 66.79 (11)° and φ = 325.26 (12)°. The dihedral angles between oxadiazol-3-ium ring (O1/N6/N7/C12/C13) and the two phenyl rings (C1–C6 and C14–C19) are 57.99 (6) and 54.48 (6)°, respectively. The correspondence angles for 1,2,4-triazole ring (N2–N4/C8/C9) are 37.35 (6) and 73.89 (6)°.

In the solid state (Fig. 2), the molecules are linked via intermolecular N1—H1···O2 and C18—H18A···N2 (Table 1) hydrogen bonds into infinite two-dimensional planes parallel to (100). The crystal structure is further consolidated by C15—H15A···Cg1 interactions (Table 1), where Cg1 is the centroid of C1–C6 phenyl ring.

Experimental

To a solution of 4-bromoacetyl-3-(p-tolyl)sydnone (0.01 mol) and 4-amino-5-[(phenylamino)methyl]-4H-1,2,4-triazole-3-thiol (0.01 mol) in ethanol, catalytic amount of anhydrous sodium acetate was added. The solution was stirred at room temperature for 2 to 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 1:2 mixtures of DMF and ethanol by slow evaporation.