4-{(Z)-2-[(E)-Benzyl­idenehydrazinyl­idene]-3,6-dihydro-2H-1,3,4-thia­diazin-5-yl}-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate

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

doi:10.1107/S1600536811010609

. 2011 Mar 26;67(Pt 4):o977–o978. doi: 10.1107/S1600536811010609

4-{(Z)-2-[(E)-Benzylidenehydrazinylidene]-3,6-dihydro-2H-1,3,4-thiadiazin-5-yl}-3-phenyl-1,2,3-oxadiazol-3-ium-5-olate

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

PMCID: PMC3100016 PMID: 21754237

Abstract

The title compound, C₁₈H₁₄N₆O₂S, exists in trans and cis configurations with respect to the two acyclic C=N bonds [bond lengths = 1.2835 (9) and 1.3049 (9) Å]. The 3,6-dihydro-2H-1,3,4-thiadiazine ring adopts a half-boat conformation. The oxadiazol-3-ium ring makes dihedral angles of 53.70 (4) and 60.26 (4)° with the two phenyl rings. In the crystal, molecules are linked via pairs of intermolecular N—H⋯N hydrogen bonds, generating R ₂ ²(8) ring motifs, and are further linked via intermolecular C—H⋯O and C—H⋯S hydrogen bonds into a three-dimensional network. The short intermolecular distance between the oxadiazol-3-ium rings [3.4154 (4) Å] indicates the existence of a π–π interaction.

Related literature

For general background to and the biological activity of sydnone derivatives, see: Newton & Ramsden (1982 ▶); Wagner & Hill (1974 ▶); Kalluraya & Rahiman (1997 ▶). For the preparation, 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

C₁₈H₁₄N₆O₂S
M _r = 378.41
Triclinic,
a = 6.8752 (2) Å
b = 10.1335 (3) Å
c = 12.7374 (4) Å
α = 78.578 (1)°
β = 88.984 (1)°
γ = 85.874 (1)°
V = 867.58 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.58 × 0.27 × 0.08 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.885, T _max = 0.982
29236 measured reflections
7567 independent reflections
6818 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.101
S = 1.03
7567 reflections
248 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.37 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/S1600536811010609/sj5123sup1.cif

e-67-0o977-sup1.cif^{(20.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010609/sj5123Isup2.hkl

e-67-0o977-Isup2.hkl^{(370.2KB, 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
N3—H1N3⋯N2ⁱ	0.852 (15)	2.015 (15)	2.8664 (9)	178.3 (11)
C14—H14A⋯O2ⁱⁱ	0.93	2.58	3.2303 (10)	127
C15—H15A⋯O2ⁱⁱⁱ	0.93	2.51	3.2391 (9)	136
C18—H18A⋯S1^iv	0.93	2.84	3.7061 (8)	155

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

Acknowledgments

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

supplementary crystallographic information

Comment

Sydnones are a class of mesoionic compounds containing a 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 with heterocyclic substituents at the 4-position are also known to exhibit 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 thiadiazine moiety was introduced at the 4-position of the phenylsydnone. A series of thiadiazines were synthesized by the condensation of 4-bromoacetyl-3-arylsydnones with N'-(phenylmethylidene)carbonohydrazide. 4-Bromoacetyl-3-arylsydnones were in turn obtained by the photochemical bromination of 4-acetyl-3-arylsydnones (Kalluraya et al., 2003).

The molecular structure is shown in Fig. 1. Bond lengths (Allen et al., 1987) and angles are within normal ranges. The title compound exists in trans and cis configurations with respect to the acyclic C7═N1 and C8═N2 bonds [C7═N1 = 1.2835 (9) Å and C8═N2 = 1.3049 (9) Å]. The 3,6-dihydro-2H-1,3,4-thiadiazine ring (S1/N3/N4/C8-C10) adopts a half boat-conformation with atom C9 deviating by 0.359 (1) Å from the mean plane through the remaining atoms, puckering parameters (Cremer & Pople, 1975) Q = 0.5575 (7) Å, Θ = 108.09 (7)° and φ = 137.99 (7)°. The oxadiazol-3-ium ring (O1/N5/N6/C11/C12) makes dihedral angles of 53.70 (4) and 60.26 (4) ° with two phenyl rings (C1-C6 and C13-C18).

In the crystal packing (Fig. 2), the molecules are linked via pairs of intermolecular N3–H1N3···N2 hydrogen bonds (Table 1), generating R₂²(8) ring motifs (Bernstein et al., 1995) and are further linked via intermolecular C14–H14A···O2, C15–H15A···O2 and C18–H18A···S1 hydrogen bonds (Table 1) into a three-dimensional network. The crystal packing is further consolidated by π-π stacking interactions between the centroids of O1/N5/N6/C11/C12 (Cg1) rings, with Cg1···Cg1^v distance of 3.4154 (4) Å [symmetry code: (v) 2-X, 2-Y, -Z].

Experimental

To a solution of 4-bromoacetyl-3-(p-anisyl)sydnone (0.01 mol) and N'-(phenylmethylidene) carbonohydrazide (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.