3-(4-Methyl­phen­yl)-4-[(thio­semi­carba­zono)meth­yl]-1,2,3-oxa­diazol-3-ium-5-olate 1,4-dioxane hemisolvate

M Abdul Rahiman; G N Ravikumar; Wan-Sin Loh; Ibrahim Abdul Razak

doi:10.1107/S1600536813008805

. 2013 Apr 13;69(Pt 5):o727. doi: 10.1107/S1600536813008805

3-(4-Methylphenyl)-4-[(thiosemicarbazono)methyl]-1,2,3-oxadiazol-3-ium-5-olate 1,4-dioxane hemisolvate

M Abdul Rahiman ^a, G N Ravikumar ^a, Wan-Sin Loh ^b,^‡, Ibrahim Abdul Razak ^b,^*,^§

PMCID: PMC3648259 PMID: 23723879

Abstract

The asymmetric unit of the title compound, C₁₁H₁₁N₅O₂S·0.5C₄H₈O₂, contains one 3-(p-tolyl)sydnone 4-thiosemicarbazone molecule and a half molecule of 1,4-dioxane, which lies abount an inversion centre. The sydnone ring is almost planar, with a maximum deviation of 0.002 (1) Å, and forms a dihedral angle of 46.31 (5)° with the benzene ring. In the crystal, the two components are linked into a tape along [01-1] by N—H⋯O and N—H⋯S hydrogen bonds. The crystal structure is further stabilized by C—H⋯O and C—H⋯π interactions, forming a three-dimensional network.

Related literature

For the biological acitivity of sydnones, see: Rai et al. (2008 ▶); Jyothi et al. (2008 ▶); Nithinchandra et al. (2012 ▶); Kalluraya et al. (2001 ▶). For a related structure, see: Fun et al. (2011 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-69-0o727-scheme1.jpg

Experimental

Crystal data

C₁₁H₁₁N₅O₂S·0.5C₄H₈O₂
M _r = 321.36
Triclinic,
a = 7.7463 (1) Å
b = 9.3776 (1) Å
c = 10.4449 (2) Å
α = 79.689 (1)°
β = 87.168 (1)°
γ = 87.461 (1)°
V = 745.09 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.35 × 0.29 × 0.24 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.921, T _max = 0.944
19865 measured reflections
5407 independent reflections
4782 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.090
S = 1.08
5407 reflections
212 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.24 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

Click here for additional data file.^{(24.9KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813008805/is5258sup1.cif

e-69-0o727-sup1.cif^{(24.9KB, cif)}

Click here for additional data file.^{(264.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008805/is5258Isup2.hkl

e-69-0o727-Isup2.hkl^{(264.7KB, hkl)}

Click here for additional data file.^{(7.1KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813008805/is5258Isup3.cml

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

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯O3ⁱ	0.872 (17)	2.040 (17)	2.8624 (12)	156.8 (14)
N5—H1N5⋯S1ⁱⁱ	0.872 (18)	2.613 (18)	3.4754 (9)	170.2 (14)
C5—H5A⋯O2ⁱⁱⁱ	0.95	2.31	3.2215 (13)	162
C9—H9A⋯O3ⁱ	0.95	2.34	3.1394 (12)	141
C12—H12B⋯O2^iv	0.99	2.56	3.2626 (14)	128
C11—H11A⋯Cg1^v	0.98	2.94	3.5736 (12)	123

Open in a new tab

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

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 the post of Research Officer under the Research University Grant (1001/PFIZIK/811160).

supplementary crystallographic information

Comment

Sydnones are mesoionic heterocyclic aromatic compounds. The study of sydnones still remains a field of interest because of their electronic structures and also because of the varied types of biological activities displayed by some of them (Rai et al., 2008). Recently sydnone derivatives were found to exhibit promising antimicrobial (Jyothi et al., 2008), anti-inflammatory (Nithinchandra et al., 2012) and CNS depressant properties (Kalluraya et al., 2001). Since their discovery, sydnones have shown diverse biological activities and it is thought that the meso-ionic nature of the sydnone ring promotes significant interactions with biological systems.

The asymmetric unit of the title compound, Fig. 1, contains one 3-(p-tolyl)-sydnone-4-thiosemicarbazone molecule and half of a 1,4-dioxane molecule. The sydnone ring (N1/N2/O1/C7/C8) is almost planar with maximum deviation of 0.002 (1) Å at O1 and it forms dihedral angle of 46.31 (5)° with the benzene ring (C1–C6).The complete 1–4 dioxane molecule is generated by crystallograhic inversion symmetry [symmetry code = -x, -y, -z + 2]. Bond lengths and angles are almost comparable with the related structure (Fun et al., 2011).

In the crystal structure, Fig. 2, the molecules are linked into three dimensional network by intermolecular N4—H1N4···O3, N5—H1N5···S1, C5—H5A···O2, C9—H9A···O3 and C12—H12B···O2 hydrogen bonds (Table 1). The crystal structure was further stabilized by C—H···π interactions (Table 1), involving the centroid of the benzene ring (Cg1).

Experimental

To a mixture of 4-formyl-3-(p-tolyl)sydnone (0.01 mol) and thiosemicarbazide (0.01 mol) in ethanol, a catalytic amount of concentrated H₂SO₄ was added. The solution was stirred at room temperature for 23 h. The solid product that separated out was filtered and dried. The recrystallization of the sample was done using an ethanol-dioxane (1:1 v/v) mixture. The slow evaporation of the ethanol-dioxane mixture of the compound resulted in crystals suitable for X-ray analysis.