(5,7-Dimethyl-2-oxo-2H-chromen-4-yl)methyl diethyl­dithio­carbamate

K Mahesh Kumar; H C Devarajegowda; S Jeyaseelan; N M Mahabaleshwaraiah; O Kotresh

doi:10.1107/S1600536812019757

. 2012 May 5;68(Pt 6):o1657. doi: 10.1107/S1600536812019757

(5,7-Dimethyl-2-oxo-2H-chromen-4-yl)methyl diethyldithiocarbamate

K Mahesh Kumar ^a, H C Devarajegowda ^b,^*, S Jeyaseelan ^b, N M Mahabaleshwaraiah ^a, O Kotresh ^a

PMCID: PMC3379255 PMID: 22719453

Abstract

In the title compound, C₁₇H₂₁NO₂S₂, the coumarin ring system is nearly planar, with a maximum deviation of 0.080 (2) Å from the mean plane. An intramolecular C—H⋯S hydrogen bond occurs. The crystal structure features C—H⋯S hydrogen bonds and weak π–π interactions with a centroid–centroid distance of 3.679 (1) Å.

Related literature

For biological applications of coumarins and dithiocarbamates, see: Smith et al. (1998 ▶); Nawrot-Modraka et al. (2006 ▶); Basanagouda et al. (2009 ▶); Kalkhambkar et al. (2007 ▶); El-Shorbagi (2000 ▶); Ronconi et al. (2006 ▶); Cvek & Dvorak (2007 ▶). For a related structure, see: Kumar et al. (2012 ▶). For the synthesis of the title compound, see: Shastri et al. (2004 ▶).

Experimental

Crystal data

C₁₇H₂₁NO₂S₂
M _r = 335.47
Monoclinic,
a = 7.8570 (2) Å
b = 23.7745 (5) Å
c = 9.7684 (2) Å
β = 109.483 (1)°
V = 1720.22 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.24 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: ψ scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.770, T _max = 1.000
14939 measured reflections
3033 independent reflections
2803 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.135
S = 1.04
3033 reflections
204 parameters
H-atom parameters constrained
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812019757/wn2474sup1.cif

e-68-o1657-sup1.cif^{(18.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019757/wn2474Isup2.hkl

e-68-o1657-Isup2.hkl^{(145.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812019757/wn2474Isup3.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
C8—H8⋯S2ⁱ	0.93	2.86	3.751 (2)	161
C16—H16C⋯S1	0.96	2.53	3.282 (3)	135

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Universities Sophisticated Instrumental Centre, Karnatak University, Dharwad, for the CCD X-ray facilities, X-ray data collection, GCMS, IR, CHNS and NMR data. KMK is grateful to Karnatak Science College, Dharwad, for providing laboratory facilities.

supplementary crystallographic information

Comment

Coumarins constitute a class of compounds which are found widely in nature and possess diverse biological activities. Over recent decades, medicinal chemists have paid great attention to the isolation, screening and structural modifications of new coumarins. They have been found to exhibit a wide range of applications in cancer, the HIV drug development arena (Smith et al., 1998), anti-tumor, anti-bacterial and cytotoxic activity (Nawrot-Modraka et al., 2006). In 4-substituted coumarins, the groups attached at the C-4 methylene carbon been shown to influence their solid state conformations, as observed in 4-aryloxymethyl (Basanagouda et al., 2009) and 4-arylaminomethyl coumarins (Kalkhambkar et al., 2007).

Dithiocarbamates have shown wide applications as pesticides,fungicides in agriculture (El-Shorbagi, 2000), potent anticancer agents (Ronconi et al., 2006), organic intermediates, rubber additives, additives of polluted water and vulcanizing agents (Cvek & Dvorak, 2007).

In view of the above observations,we proposed that 4-substituted coumarins bearing the dithiocarbamate (DTC)group should display some interesting biological activity and the title compound was screened for fungicidal, bacterial and DNA cleavage properties.The crystal structure of a coumarin derivative linked to the DTC group has been reported (Kumar et al., 2012).

The title compound is one of a series of dithiocarbamate coumarins with potential as possible anti-microbial agents. For these reasons, in continuation of our interest in the crystal structures of coumarin derivatives, we report here its crystal structure.

The asymmetric unit of 5,7-dimethyl-2-oxo-2H-chromen-4-yl)methyl diethyldithiocarbamate is shown in Fig. 1.The coumarin ring system (O3/C6–C14) is nearly planar, with a maximum deviation from the mean plane of 0.080 (2) Å for atom C12.

In the crystal structure (Fig. 2), the molecules are connected via weak intramolecular C8—H8···S2 and intermolecular C16—H16C···S1 hydrogen bonds (Table 1). Furthermore, the crystal structure features π-π stacking interactions between the pyran ring (O3/C10–C14; centroid Cg1) and the benzene ring (C6–C11; centroid Cg2), with a Cg1···Cg2 distance of 3.679 (1) Å.

Experimental

All the chemicals were of analytical reagent grade and were used directly without further purification. 4-Bromomethyl coumarin required for the synthesis of the target molecule was synthesized according to an already reported procedure involving Pechmann cyclization of phenols with 4-bromoethyl acetoacetate (Shastri et al., 2004) and sodium diethyldithiocarbamate purchased from Sigma- Aldrich.

A mixture of 2.6 g (0.01 mol) of 5,7-dimethyl-4-bromomethylcoumarin and 1.71 g (0.01 mol) of sodium diethyldithiocarbamate in 30 ml dry alcohol was stirred for 24 h at room temperature (the reaction was monitored by TLC). The solvent was evaporated and the resulting solid was extracted twice with a dichloromethane-H₂O mixture. The organic layer was dried over anhydrous CaCl₂ and evaporation of the organic solvent gave the title compound. The compound was recrystallized from an ethanol-chloroform mixture. Colour: Colourless. Yield: 91%. M.P.: 409 K.