(2-Oxo-2H-benzo[h]chromen-4-yl)methyl morpholine-4-carbodithio­ate

Rajni Kant; Vivek K Gupta; Kamini Kapoor; Gurvinder Kour; K Mahesh Kumar; N M Mahabaleshwaraiah; O Kotresh

doi:10.1107/S160053681201094X

. 2012 Mar 17;68(Pt 4):o1104–o1105. doi: 10.1107/S160053681201094X

(2-Oxo-2H-benzo[h]chromen-4-yl)methyl morpholine-4-carbodithioate

Rajni Kant ^a,^*, Vivek K Gupta ^a, Kamini Kapoor ^a, Gurvinder Kour ^a, K Mahesh Kumar ^b, N M Mahabaleshwaraiah ^b, O Kotresh ^b

PMCID: PMC3344054 PMID: 22589963

Abstract

In the title compound, C₁₉H₁₇NO₃S₂, the morpholine ring is in a chair conformation. In the coumarin ring system, the dihedral angle between the benzene and pyran rings is 3.9 (1)°. In the crystal, weak C—H⋯O interactions link the molecules into corrugated layers parallel to (102). The crystal packing also exhibits π–π interactions, with distances of 3.644 (1) and 3.677 (1) Å between the centroids of the benzene rings of neighbouring molecules.

Related literature

For the biological activity of coumarins, see: Kontogiorgis & Hadjipavlou-Litina (2004 ▶). For a related structure, see: Kumar et al. (2012 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₉H₁₇NO₃S₂
M _r = 371.46
Monoclinic,
a = 13.0928 (4) Å
b = 11.6978 (3) Å
c = 11.3673 (3) Å
β = 99.232 (3)°
V = 1718.43 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.818, T _max = 1.000
18655 measured reflections
3017 independent reflections
2457 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.104
S = 1.05
3017 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681201094X/cv5260sup1.cif

e-68-o1104-sup1.cif^{(25.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201094X/cv5260Isup2.hkl

e-68-o1104-Isup2.hkl^{(145KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681201094X/cv5260Isup3.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—H9⋯O3ⁱ	0.93	2.42	3.346 (3)	173
C18—H18A⋯O2ⁱⁱ	0.97	2.56	3.466 (3)	155

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

Acknowledgments

RK acknowledges the Department of Science & Technology for the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. He is also thankful to the University of Jammu, Jammu, India, for financial support.

supplementary crystallographic information

Comment

Coumarins (2H-1-benzopyran-2-ones) form a distinct class of oxygen containing heterocycles and are widely distributed in nature. Coumarins represent a class of naturally and synthetically obtained compounds that possess a wide variety of biological activities. Specifically coumarins are reported to possess antiallergic, anticoagulant, antidiabetic activities and analgesic properties (Kontogiorgis & Hadjipavlou-Litina, 2004). In continuation of our interest on crystal structures study of coumarin derivatives (Kumar et al., 2012), we report the crystal structure of the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are within normal ranges (Allen et al., 1987) and are in a good agreement with those in related structure (Kumar et al., 2012). The morpholine ring adopts a chair conformation. The dihedral angle bewteen the pyran and benzene rings in the coumarin fragment is 3.9 (1)°. Weak intermolecular C—H···O interactions (Table 1)link the molecules into corrugated layers parallel to (102) plane. The crystal packing exhibits π-π stacking interactions. The first of these is between the benzene ring C4/C5/C10-C13 and its symmetry-related partner at (1-x, 1-y, -z) with a distance of 3.644 (1) Å between the ring centroids. Another π-π interaction is between the benzene ring C4/C5/C10-C13 and the benzene ring C5-C10 at (1-x, 1-y,-z) with a distance of 3.677 (1) Å between the ring centroids.

Experimental

A mixture of 2.73g (0.01 mol) of 7,8-benzo- 4-bromomethyl coumarin and 2.00g (0.01 mol) of potassium salt of morpholine-1-dithiocarbomate in 30 ml dry alcohol was stirrer for 12 hours at room temperature (the reaction was monitored by TLC). The solvent was evaporated and the solid was extracted twice with MDC –water mixture. The organic solvent was dried over CaCl2, evaporated the solvent and recrystallised from ethanol-chloroform. A slow evaporation technique was used to grow crystals suitable for diffraction studies in an ethanol-chloroform mixture. Yield=89%, m.p.-182-84oC. IR(KBr): 1717cm-1(C=O), 1423.8cm-1 (C=S), 849cm-1(C-N), 1111.7 (C-O-C).GCMS: m/e: 371.06. 1H- NMR(300MHz, CdCl3,δppm):2.81(s, 4H, C13 & C17-H), 1.73(s, 8H, C16,C17, C18 & C19-H), 4.32 (s,2H, C4-CH2), 7.26 (s,1H, C2-H), 7.45 (d,1H, C12-H), 7.63 (t,1H, C11-H), 7.66 (t,1H, C8-H), 7.91 (d,1H, C7-H), 7.97 (d,1H, C9-H), 8.47 (d,1H C6-H).Elemental analysis: C, 61.40; H, 4.56; N, 3.73; O, 12.90; S, 16.8 M.P.: