Crystal structure of (6-bromo-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodi­thio­ate

K Mahesh Kumar; K R Roopashree; M Vinduvahini; O Kotresh; H C Devarajegowda

doi:10.1107/S2056989015011007

. 2015 Jun 13;71(Pt 7):o489–o490. doi: 10.1107/S2056989015011007

Crystal structure of (6-bromo-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodithioate

K Mahesh Kumar ^a, K R Roopashree ^b, M Vinduvahini ^c, O Kotresh ^a, H C Devarajegowda ^b,^*

PMCID: PMC4518962 PMID: 26279923

Abstract

In the title compound, C₁₅H₁₄BrNO₃S₂, the 2H-chromene ring system is nearly planar, with a maximum deviation of 0.034 (2) Å, and the morpholine ring adopts a chair conformation. The dihedral angle between best plane through the 2H-chromene ring system and the morpholine ring is 86.32 (9)°. Intramolecular C—H⋯S hydrogen bonds are observed. In the crystal, inversion-related C—H⋯S and C—H⋯O interactions generate R ₂ ²(10) and R ₂ ²(8) rings patterns, respectively. In addition, the crystal packing features π–π interactions between fused benzene rings [centroid–centroid distance = 3.7558 (12) Å].

Keywords: crystal structure, coumarins, dithiocarbamates, biological applications, hydrogen bonding, π–π interactions

Related literature

For biological applications of coumarins and dithiocarbamates, see: D’hooghe & De Kimpe (2006 ▸); Hesse & Kirsch (2002 ▸); Jung et al. (2001 ▸, 2004 ▸); Lee et al. (1998 ▸); Melagraki et al. (2009 ▸); Schönenberger & Lippert (1972 ▸). For standard bond lengths, see: Devarajegowda et al. (2013 ▸). For a related structure and the synthesis of the title compound, see: Devarajegowda et al. (2013 ▸). graphic file with name e-71-0o489-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₄BrNO₃S₂
M _r = 400.30
Triclinic,
a = 7.0500 (3) Å
b = 7.6049 (3) Å
c = 15.1376 (7) Å
α = 78.782 (2)°
β = 88.549 (2)°
γ = 78.515 (2)°
V = 780.07 (6) Å³
Z = 2
Mo Kα radiation
μ = 2.91 mm⁻¹
T = 296 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
13789 measured reflections
3224 independent reflections
2806 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.065
S = 1.03
3224 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.43 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: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL2014.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015011007/bq2399sup1.cif

e-71-0o489-sup1.cif^{(557.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011007/bq2399Isup2.hkl

e-71-0o489-Isup2.hkl^{(257.4KB, hkl)}

Click here for additional data file.^{(5.8KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015011007/bq2399Isup3.cml

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989015011007/bq2399fig1.tif

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen atoms are shown as spheres of arbitrary radius.

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989015011007/bq2399fig2.tif

Crystal packing for the title compound with hydrogen bonds drawn as dashed lines.

CCDC reference: 1405247

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C17H17AO5ⁱ	0.97	2.53	3.501(2)	176
C17H17BS3	0.97	2.55	3.1633(16)	121
C19H19AS2	0.97	2.37	2.864(2)	111
C22H22BS3	0.97	2.61	3.0486(19)	108

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Universities Sophisticated Instrumental Centre, Karnatak University, Dharwad, for access to the CCD X-ray facilities, X-ray data collection, GCMS, IR, CHNS and NMR data.

supplementary crystallographic information

S1. Comment

In recent years, much attention has been directed towards the synthesis of substituted coumarins owing to their tremendous application in various research fields including biological science and medicinal chemistry. Substituted coumarin derivatives are components of numerous natural products like warfarin, phenprocoumon, coumatetralyl, carbochromen, bromadialone, etc. These compounds also exhibit a wide band of biological activities including antibacterial, anti-HIV (Hesse & Kirsch, 2002), antiviral (Lee et al., 1998), anticoagulant (Jung et al., 2001), antioxidant (Melagraki et al., 2009) and anticancer activities (Jung et al.,(2004). Carbon–sulfur bond formation is a fundamental approach to bring sulfur into organic compounds, and this has received much attention due to its occurrence in many molecules that are of biological and pharmaceutical importance. The antibacterial and antifungal activities of dithiocarbamates were reported to arise by the reaction with HS-groups of the physiologically important enzymes by transferring the alkyl group of the dithioester to the HS-function of the enzyme (Schönenberger & Lippert, 1972). Organic dithiocarbamates, ubiquitously found in a variety of biologically active molecules (Dhooghe & De Kimpe, 2006), are of high importance in academia as well as in industry.

In view of the various physiological activities of coumarins and dithiocarbamates, our current studies are focused on the development of new routes for the synthesis of coumarins incorporating dithiocarbamate moieties.

The asymmetric unit of (6-bromo-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodi thioate is shown in Fig. 1. The 2H-chromene ring systems is nearly planar, with a maximum deviation of 0.0337 (23) Å for the atom C16 and the morpholine ring adopts a chair conformation. The dihedral angle between the 2H-chromene ring and the morpholine ring is 86.32 (9) °. In the crystal structure, intermolecular C—H···O and intramolecular C–H···S hydrogen bonds are observed (Table 1) and inversion related C—H···S and C—H···O interactions generate R₂²(10) and R₂²(8) rings pattern respectively. In addition, the crystal packing is stabilized by π–π [C_g (3)– C_g(3);C8–C13] interactions between fused benzene rings [centroid- centroid distance = 3.7558 (12)].

S2. Experimental

All the chemicals used were of analytical reagent grade and were used directly without further purification. The title compound was synthesized according to the reported method (Devarajegowda et al., 2013). The compound is recrystallized by ethanol-chloroform mixture. Colourless needles of the title compound were grown from a mixed solution of Ethanol/Chloroform (V/V = 2/1) by slow evaporation at room temperature. Yield =72%, m.p.: 433–435 K