4-{2-[2-(4-Chloro­benzyl­idene)hydrazinyl­idene]-3,6-dihydro-2H-1,3,4-thia­diazin-5-yl}-3-phenyl­sydnone

Hoong-Kun Fun; Wan-Sin Loh; Nithinchandra; Balakrishna Kalluraya

doi:10.1107/S1600536811013912

. 2011 Apr 22;67(Pt 5):o1177–o1178. doi: 10.1107/S1600536811013912

4-{2-[2-(4-Chlorobenzylidene)hydrazinylidene]-3,6-dihydro-2H-1,3,4-thiadiazin-5-yl}-3-phenylsydnone

Hoong-Kun Fun ^a,^*,^‡, Wan-Sin Loh ^a,^§, Nithinchandra ^b, Balakrishna Kalluraya ^b

PMCID: PMC3089094 PMID: 21754481

Abstract

The title compound, C₁₈H₁₃ClN₆O₂S, exists in trans and cis configurations with respect to the acyclic C=N bonds [C=N = 1.2837 (15) and 1.3000 (14) Å, respectively]. The 3,6-dihydro-2H-1,3,4-thiadiazine ring adopts a half-boat conformation. The sydnone ring is approximately planar [maximum deviation = 0.002 (1) Å] and forms dihedral angles of 50.45 (7) and 61.21 (6)° with the aromatic rings. In the crystal, intermolecular N—H⋯N, C—H⋯Cl and C—H⋯S hydrogen bonds link the molecules into layers parallel to ab plane. The crystal packing is stabilized by C—H⋯π interactions and further consolidated by π–π interactions involving the phenyl rings [centroid–centroid distance = 3.6306 (7) Å].

Related literature

For background to sydnones and their biological activity, see: Newton & Ramsden (1982 ▶); Wagner & Hill (1974 ▶); Kalluraya & Rahiman (1997 ▶); Kalluraya et al. (2003 ▶). For related structures, see: Fun et al. (2010 ▶); Fun, Loh et al. (2011 ▶); Fun, Quah et al. (2011 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₈H₁₃ClN₆O₂S
M _r = 412.85
Triclinic,
a = 7.3180 (3) Å
b = 10.1567 (5) Å
c = 12.4721 (6) Å
α = 96.686 (1)°
β = 95.285 (1)°
γ = 95.229 (1)°
V = 911.92 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 100 K
0.51 × 0.23 × 0.07 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.842, T _max = 0.976
18115 measured reflections
6480 independent reflections
5506 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.113
S = 1.05
6480 reflections
257 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.27 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/S1600536811013912/bq2294sup1.cif

e-67-o1177-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013912/bq2294Isup2.hkl

e-67-o1177-Isup2.hkl^{(317.1KB, hkl)}

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

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

Cg2 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1N3⋯N2ⁱ	0.84 (2)	2.03 (2)	2.8752 (14)	178 (2)
C9—H9A⋯Cl1ⁱⁱ	0.97	2.78	3.4904 (13)	130
C18—H18A⋯S1ⁱⁱⁱ	0.93	2.86	3.6729 (12)	147
C17—H17A⋯Cg2^iv	0.93	2.64	3.5208 (15)	158

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

Acknowledgments

The authors thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). WSL also thanks the Malaysian Government and USM for the award of a research fellowship.

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 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 thiadiazine moiety at the 4-position of the phenylsydnone was introduced. The title compound was synthesized by the condensation of 4-bromoacetyl-3-arylsydnones with N'-[(4-chlorophenyl)methylidene]thiocarbonohydrazide. 4-Bromoacetyl-3-arylsydnones were in turn obtained by the photochemical bromination of 4-acetyl-3-arylsydnones (Kalluraya et al., 2003).

The title compound (Fig. 1) exists in trans and cis configurations with respect to the acyclic C7═N1 and C8═N2 bonds [C7═N1 = 1.2837 (15) Å and C8═N2 = 1.3000 (14) Å], respectively. The 3,6-dihydro-2H-1,3,4-thiadiazine ring (N3/N4/C10/C9/S1) adopts a half-boat conformation with the puckering parameter (Cremer & Pople, 1975), Q = 0.5266 (11) Å; Θ = 108.31 (12)°; φ = 138.02 (13)°. The sydnone ring (N5/N6/O1/C12/C11) is approximately planar with a maximum deviation of 0.002 (1) Å at atom N5 and forms dihedral angles of 50.45 (7)° and 61.21 (6)° with the phenyl rings (C1–C6 & C13–C18), respectively. Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to the related structures (Fun et al., 2010; Fun & Loh et al., 2011; Fun & Quah et al., 2011).

In the crystal packing (Fig. 2), intermolecular N3—H1N3···N2, C9—H9A···Cl1 and C18—H18A···S1 hydrogen bonds (Table 1) link the molecules into layers parallel to ab plane. The crystal packing is stabilized by C—H···π interactions (Table 1) and further consolidated by π–π interactions (Table 1), involving the centroids of phenyl rings (Cg1; C13–C18) with the separation of Cg1···Cg1^v being 3.6306 (7) Å [symmetry code: (v) -1 - x, -y, 1 - z].

Experimental

To a solution of 4-bromoacetyl-3-(p-anisyl)sydnone (0.01 mol) and N'-[(4-chlorophenyl)methylidene]thiocarbonohydrazide (0.01 mol) in ethanol, a catalytic amount of anhydrous sodium acetate was added. The solution was stirred at room temperature for 2–3 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.