5,5′-[1,4-Phenyl­enebis(methyl­enesulfanedi­yl)]bis­[1,3,4-thia­diazol-2(3H)-one] dimethyl sulfoxide disolvate

Sung Kwon Kang; Nam Sook Cho; Siyoung Jang

doi:10.1107/S1600536812006289

. 2012 Feb 17;68(Pt 3):o781. doi: 10.1107/S1600536812006289

5,5′-[1,4-Phenylenebis(methylenesulfanediyl)]bis[1,3,4-thiadiazol-2(3H)-one] dimethyl sulfoxide disolvate

Sung Kwon Kang ^a,^*, Nam Sook Cho ^a, Siyoung Jang ^a

PMCID: PMC3297851 PMID: 22412654

Abstract

The asymmetric unit of the title compound, C₁₂H₁₀N₄O₂S₄·2C₂H₆OS, contains one half of the p-xylene molecule and one dimethyl sulfoxide molecule. The p-xylene molecule is located about a crystallographic inversion centre. In the molecule, the thiadiazole and benzene rings are almost perpendicular to one another, with a dihedral angle of 88.95 (6)°. In the crystal, an N—H⋯O hydrogen bond is observed between the two components. The dimethyl sulfoxide molecule is disordered over two orientations with an occupancy ratio of 0.879 (1):0.121 (1).

Related literature

For general background to polydentate macrocyclic compounds, see: Dietrich et al. (1993 ▶); Vogle (1991 ▶). For the synthesis and reactivity of thiadiazole derivatives, see: Cho et al. (1998 ▶, 1999 ▶, 2001 ▶).

Experimental

Crystal data

C₁₂H₁₀N₄O₂S₄·2C₂H₆OS
M _r = 526.74
Triclinic,
a = 7.5723 (15) Å
b = 8.3258 (17) Å
c = 10.346 (2) Å
α = 109.70 (4)°
β = 95.74 (3)°
γ = 91.15 (3)°
V = 610.0 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 296 K
0.18 × 0.17 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.895, T _max = 0.923
21342 measured reflections
3039 independent reflections
2124 reflections with I > 2σ(I)
R _int = 0.083

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.100
S = 1.02
3039 reflections
162 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812006289/is5071sup1.cif

e-68-0o781-sup1.cif^{(20.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006289/is5071Isup2.hkl

e-68-0o781-Isup2.hkl^{(146.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812006289/is5071Isup3.cml

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—H3⋯O13	0.91 (2)	1.83 (2)	2.742 (3)	175.6 (19)

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supplementary crystallographic information

Comment

Polydentate macrocyclic compounds containing heterocyclic rings as subunits possess a variety of interesting properties. Heterocyclic units contain oxygen, nitrogen or sulfur, which provide the coordination sites allowing the heterocycles to form complexes with metals and act as effective hosts for different kinds of molecules (Dietrich et al., 1993; Vogle, 1991). We studied on macrocyclic compounds composed of two 5-mercapto-2,3-dihydro-1,3,4-thiadizol-2-ones and two p-xylenes (Cho et al., 1998, 1999, 2001). The NH of the title compound, α,α'-bis[(4,5-dihydro-5-oxo-1,3,4-thiazol-2-yl)thio]-p-xylene (I) is acidic enough to be alkylated in triethylamine with alkyl halide. The two NH functional groups can afford ring formation through an [2 + 2] alkylation.

The 5-oxo-1,3,4-thiadiazol-2-yl unit is planar, with an r.m.s. deviation of 0.004 Å from the corresponding squares plane defined by the seven constituent atoms. There is a crystallographic inversion center located in the middle of benzene ring. The bond distance of N4—C5 [1.281 (2) Å] is shorter than that of C2—N3 [1.337 (2) Å], which is consistent with double bond character. The thiadiazole and benzene rings are almost perpendicular to each other, with a dihedral angle 88.95 (6)°. The crystal structure is stabilized by the intermolecular N—H···O hydrogen bonds between the p-xylene compound and the dimethyl sulfoxide molecules (Fig. 1 and Table 1).

Experimental

To a solution of α,α'-bis[(5-ethoxy-1,3,4-thiadiazol-2-yl)thio]-p-xylene (Cho et al., 1999, 2001) (2.56 g, 6 mmol) in ethanol (20 ml), was added HBr (47%, 3.5 ml, 30 mmol), in one portion. The mixture was heated under reflux until the above p-xylene compound was disappeared on TLC. The solvent evaporated under reduced pressure to leave a solid residue, which was washed with water. The crude product was recrystallized from EtOH:THF = 3:1. Colorless crystals of (I) were obtained from its DMSO solution by slow evaporation of the solvent at room temperature. Yield 92%, m.p. 208–210°C; R_f: 0.63 (n-hexane: EA = 5: 5); IR (KBr pellet, cm^-1): 3120 (NH), 3062, 2950 (CH), 1656 (C═O), 1500, 1200; ¹H NMR (DMSO-d₆, p.p.m.): 12.95(2H, s, NH), 7.35(4H, s, C₆H₄), 4.32(4H, s, SCH₂); ¹³C NMR (DMSO-d₆, p.p.m.): 171.4 (C=O), 147.8 (C—S), 135.9, 129.2, (C₆H₄), 36.2 (SCH₂).