(5,7-Dimethyl-2-oxo-2H-chromen-4-yl)methyl pyrrolidine-1-carbodithio­ate

N M Mahabaleshwaraiah; K Mahesh Kumar; O Kotresh; Waleed Fadl Ali Al-eryani; H C Devarajegowda

doi:10.1107/S1600536812018004

. 2012 May 2;68(Pt 6):o1584. doi: 10.1107/S1600536812018004

(5,7-Dimethyl-2-oxo-2H-chromen-4-yl)methyl pyrrolidine-1-carbodithioate

N M Mahabaleshwaraiah ^a, K Mahesh Kumar ^a, O Kotresh ^a, Waleed Fadl Ali Al-eryani ^b, H C Devarajegowda ^b,^*

PMCID: PMC3379197 PMID: 22719395

Abstract

In the title compound, C₁₇H₁₉NO₂S₂, the 2H-chromene ring system is almost planar, with a maximum deviation of 0.044 (2) Å, and the pyrrolidine ring adopts an envelope conformation. The dihedral angle between the 2H-chromene system and the planar part of the pyrrolidine ring is 83.65 (8)°. A weak intramolecular C—H⋯S hydrogen bond occurs. The crystal structure features C—H⋯O hydrogen bonds and π–π interactions, with a centroid–centroid distance of 3.5728 (16) Å.

Related literature

For biological properties of coumarins, see: Adavi et al. (2004 ▶); Laurin et al. (1999 ▶); Kulkarni et al. (2006 ▶). For related structures, see: Kumar et al. (2012 ▶); Kant et al. (2012 ▶). For synthetic details, see: Shastri et al. (2004 ▶); Vasilliev & Polackov (2000 ▶).

Experimental

Crystal data

C₁₇H₁₉NO₂S₂
M _r = 333.45
Monoclinic,
a = 13.7023 (4) Å
b = 15.9082 (4) Å
c = 7.5511 (2) Å
β = 103.358 (1)°
V = 1601.45 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.34 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
12677 measured reflections
2805 independent reflections
2410 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.099
S = 1.07
2805 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.26 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/S1600536812018004/wn2472sup1.cif

e-68-o1584-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812018004/wn2472Isup2.hkl

e-68-o1584-Isup2.hkl^{(134.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812018004/wn2472Isup3.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
C11—H11B⋯S2	0.97	2.51	3.172 (2)	126
C18—H18⋯O4ⁱ	0.93	2.52	3.411 (3)	161
C22—H22C⋯S1	0.96	2.81	3.564 (2)	137

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the Universities Sophisticated Instrumental Centre, Karnatak University, Dharwad, for CCD X-ray facilities, single-crystal X-ray diffractometer, GCMS, IR, CHNS and NMR data. NMM is grateful to Karnatak Science College, Dharwad, for providing laboratory facilities. He is also thankful to P C Jabin Science College, Hubli and UGC for allowing him to do research under FIP.

supplementary crystallographic information

Comment

Coumarins are a class of naturally occurring lactones. A number of coumarins have been isolated in recent years, mainly from plant sources and extracts of these have been employed as traditional medicines in different areas of the world. Coumarin derivatives with various thio substituents at the C-4 position have revealed potential as antibacterial (Adavi et al., 2004), DNA gyrase studies (Laurin et al., 1999) and anticancer activity (Kularni et al., 2006).

In our present work, we have been able to link a dithiocarbamate group at the C-4 methylene carbon and it was deemed of considerable interest to study the effect of this group on the total solid state conformation of the molecule. The synthesized compound was screened for antimicrobial, antidiabetic, DNA binding and DNA cleavage studies.In continuation of our interest in the crystal structures of coumarin derivatives (Kumar et al., 2012; Kant et al., 2012), we report here the crystal structure of the title compound.

The asymmetric unit of (5,7-dimethyl-2-oxo-2H-chromen-4-yl)methyl pyrrolidine-1-carbodithioate is shown in Fig. 1. The 2H-chromene ring system (O3/C12–C20) is essentially planar, with a maximum deviation of 0.044 (2)Å for atom C15.The pyrrolidine ring adopts an envelope conformation with C8 as the flap atom. The dihedral angle between the 2H-chromene ring system (O3/C12–C20) and the planar part of the pyrrolidine ring (N5, C6, C7, C9) is 83.65 (8)°.

In the crystal structure, (Fig. 2), the molecules are connected via weak intramolecular C11—H11B···S2 and C22—H22C···S1 and intermolecular C—H···O hydrogen bonds (Table 1).Furthermore, the crystal structure features a π-π interaction,with a centroid Cg2 (O3/C12–C16) to centroid Cg3 (C13/C14/C17–C20) distance of 3.5728 (16) Å.

Experimental

All the chemicals used 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 pyrrolidine-1-carbodithioate was synthesized according to the reported procedure (Vasilliev & Polackov, 2000). A mixture of 2.67 g (0.01 mol) of 5,7-dimethyl-4-bromomethyl coumarin and1.69 g (0.01 mol) of sodium pyrrolidine-1-carbodithioate 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 88%, m.p.443 K.