(E)-[2-(1,3-Dithio­lan-2-yl­idene)hydrazinyl­idene](3-fluoro­phen­yl)methyl 3-fluoro­benzoate

Ling Yin

doi:10.1107/S1600536813007319

. 2013 Mar 23;69(Pt 4):o571. doi: 10.1107/S1600536813007319

(E)-[2-(1,3-Dithiolan-2-ylidene)hydrazinylidene](3-fluorophenyl)methyl 3-fluorobenzoate

Ling Yin ^a,^*

PMCID: PMC3629619 PMID: 23634106

Abstract

In the title compound, C₁₇H₁₂F₂N₂O₂S₂, the conformation of the dithiacyclopentane ring is a half-chair, with a total puckering amplitude Q _T = 0.460 (1) Å. π–π interactions [centroid–centroid distance = 3.585 (9) Å between the fluorophenyl rings of neighbouring molecules] and C—H⋯N and C—H⋯O interactions help to stabilize the crystal structure and form ladders along the c axis.

Related literature

For the use of dithiolan heterocyclic compounds as broad-spectrum fungicides, see: Tanaka et al. (1976 ▶); Wang et al. (1994 ▶). graphic file with name e-69-0o571-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₂F₂N₂O₂S₂
M _r = 378.41
Triclinic,
a = 9.124 (4) Å
b = 9.757 (4) Å
c = 10.738 (4) Å
α = 104.592 (3)°
β = 110.326 (5)°
γ = 101.194 (4)°
V = 824.6 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 113 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2009) ▶ T _min = 0.932, T _max = 0.932
7057 measured reflections
2896 independent reflections
2098 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.076
S = 0.96
2896 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CrystalClear-SM Expert (Rigaku/MSC, 2009) ▶; cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(18.8KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813007319/hg5300sup1.cif

e-69-0o571-sup1.cif^{(18.8KB, cif)}

Click here for additional data file.^{(142.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007319/hg5300Isup2.hkl

e-69-0o571-Isup2.hkl^{(142.1KB, hkl)}

Click here for additional data file.^{(6.3KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813007319/hg5300Isup3.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
C9—H9B⋯O2ⁱ	0.97	2.49	3.280 (2)	138
C10—H10B⋯O2ⁱⁱ	0.97	2.46	3.248 (2)	138
C13—H13A⋯N1ⁱⁱⁱ	0.93	2.50	3.424 (3)	176

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

Acknowledgments

The author thanks the Jining University Foundation (No. 2012YYJJ07) for financial support of this work.

supplementary crystallographic information

Comment

Many dithiolan heterocyclic compounds have been widely used as potent and broad-spectrum fungicides (Tanaka et al., 1976; Wang et al., 1994). In order to search for new heterocylic compounds with higher biological activities, we synthesized the (E)-((1,3-dithiolan-2-yl)diazenyl)(3-fluorophenyl)methyl 3-fluorobenzoate and describe its structure here.

In the title compound, C₁₇H₁₂F₂N₂O₂S₂, the conformation of the dithiacyclopentane ring (C8—C10/S1—S2) is halfchair, with a total puckering amplitude Q_T = 0.460 (1) Å. π-π interactions (centroid-to-centroid distances 3.585 (9) Å between the fluorophenyl rings (C12—C17) of neighbouring molecules) and intermolecular C—H···N and C—H···O interactions help to stabilize the crystal structure (Table 1).

Experimental

1.34 g (10 mmol) of (1,3-dithiolan-2-ylidene)hydrazine and 20 mmol triethylamine was dissolved in 15 ml of dichloromethane and stirred at room temperature, 3.17 g (20 mmol) 3-fluorobenzoyl chloride was added dropwise to the mixture. The reaction mixture was stirred vigorously at 273 K for 3 h. The reaction mixture was poured into 200 ml of water and extracted with three 50-ml portions of dichloromethane. The combined extracts were washed with saturated brine, dried over anhydrous sodium sulfate and evaporated on a rotary evaporator to afford the crude product, which was purified by column chromatography to yield the pure product as colorless crystals. Single crystals suitable for X-ray diffraction were obtained through slow evaporation of a solution of the pure title compound in ethanol.