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

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

doi:10.1107/S1600536811013900

. 2011 Apr 22;67(Pt 5):o1175–o1176. doi: 10.1107/S1600536811013900

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

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

PMCID: PMC3089192 PMID: 21754480

Abstract

The title compound, C₁₉H₁₅ClN₆O₃S, exists in trans and cis configurations with respect to the acyclic C=N bonds. The 3,6-dihydro-2H-1,3,4-thiadiazine ring adopts a half-boat conformation. The sydnone ring is approximately planar [maximum deviation = 0.013 (1) Å] and forms dihedral angles of 34.76 (4) and 48.67 (4)° with the benzene rings. An intramolecular C—H⋯O hydrogen bond stabilizes the molecular structure and forms an S(6) ring motif. In the crystal packing, intermolecular N—H⋯N hydrogen bonds link centrosymmetrically related molecules into dimers, generating R ₂ ²(8) ring motifs. The dimers are then linked into a three-dimensional network by intermolecular C—H⋯O and C—H⋯Cl hydrogen bonds, and by C—H⋯π interactions. Further stabilization is provided by π–π interactions involving the sydnone rings, with centroid–centroid separations of 3.4198 (5) Å.

Related literature

For background to and the biological activity of sydnones, see: Baker et al. (1949 ▶); Hedge et al. (2008 ▶); Rai et al. (2008 ▶); Kalluraya et al. (2003 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For related structures, see: Fun et al. (2010 ▶, 2011 ▶). 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

C₁₉H₁₅ClN₆O₃S
M _r = 442.88
Monoclinic,
a = 7.2322 (2) Å
b = 22.7311 (6) Å
c = 12.9299 (3) Å
β = 114.426 (1)°
V = 1935.37 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 100 K
0.56 × 0.33 × 0.19 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009) ▶ T _min = 0.832, T _max = 0.937
38523 measured reflections
10172 independent reflections
8764 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.088
S = 1.03
10172 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.31 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/S1600536811013900/rz2581sup1.cif

e-67-o1175-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013900/rz2581Isup2.hkl

e-67-o1175-Isup2.hkl^{(497.4KB, hkl)}

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

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

Cg2 is the centroid of the N3/N4/C10/C9/S1 thiadiazine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯N2ⁱ	0.88	2.00	2.8841 (9)	174
C1—H1A⋯O2ⁱⁱ	0.93	2.59	3.4898 (10)	162
C9—H9B⋯O2	0.97	2.41	3.0433 (10)	123
C18—H18A⋯Cl1ⁱⁱⁱ	0.93	2.77	3.6978 (7)	173
C19—H19B⋯Cg2^iv	0.96	2.79	3.5792 (11)	140

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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 constitute a well defined class of mesoionic compounds consisting of the 1,2,3-oxadiazole ring system. The introduction of the concept of mesoionic structure for certain heterocyclic compounds in the year 1949 has proved to be a fruitful development in heterocyclic chemistry (Baker et al., 1949). The study of sydnones still remains a field of interest because of their electronic structures and also because of the various types of biological activities displayed by some of them. Interest in sydnone derivatives has also been encouraged by the discovery that they exhibit various pharmacological activities (Hedge et al., 2008; Rai et al., 2008).

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-chlorohlorophenyl)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 = 1.2842 (9) Å and C8═N2 = 1.3061 (9) 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 parameters (Cremer & Pople, 1975), Q = 0.5322 (7) Å, Θ = 108.60 (8)°, φ = 136.74 (8)°. The sydnone ring (N5/N6/O1/C12/C11) is approximately planar with a maximum deviation of 0.013 (1) Å at atom C12 and forms dihedral angles of 34.76 (4) and 48.67 (4)° with the benzene rings (C1–C6 and C13–C18), respectively. An intramolecular C9—H9B···O2 hydrogen bond (Table 1) stabilizes the molecular structure and forms an S(6) ring motif (Bernstein et al., 1995). Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to the related structures (Fun et al., 2010; Fun et al., 2011).

In the crystal packing (Fig. 2), intermolecular N3—H1···N2 hydrogen bonds (Table 1) link centrosymmetrically related molecules to form dimers, generating R₂²(8) ring motifs (Bernstein et al., 1995). The dimers are then linked into a three-dimensional network by intermolecular C1—H1A···O2 and C18—H18A···Cl1 hydrogen bonds (Table 1) and stabilized by C—H···π interactions. The crystal structure is further consolidated by π–π interactions (Table 1), involving the sydnone rings (Cg1) with centroid-to-centroid separations Cg1···Cg1^v = 3.4198 (5) Å [symmetry code: (v) 2 - x,2 - y,1 - z].

Experimental

To a solution of 4-bromoacetyl-3-(4-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 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 by slow evaporation of a DMF/ethanol solution (1:2 v/v).