(7-Chloro-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbodithio­ate

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

doi:10.1107/S1600536812007933

. 2012 Feb 29;68(Pt 3):o878–o879. doi: 10.1107/S1600536812007933

(7-Chloro-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbodithioate

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

PMCID: PMC3297927 PMID: 22412730

Abstract

In the title compound, C₁₆H₁₆ClNO₂S₂, the piperidine ring is in a chair conformation. In the coumarin ring system, the dihedral angle between the benzene and pyran rings is 3.5 (1)°. In the crystal, a weak C—H⋯O hydrogen bond links molecules into chains along [001]. In addition, π–π stacking interactions are present involving the benzene and pyran rings, with a centroid-to-centroid distance of 3.712 (2) Å. The crystal studied is a nonmerohedral twin with refined components 0.221 (1) and 0.779 (1).

Related literature

For structures and properties of coumarins, see: Kulkarni et al. (2006 ▶); Jones et al. (1985 ▶); Trenor et al. (2004 ▶); Hung et al. (2007 ▶). For the applications of dithiocarbamate compounds, see: Bergendorff & Hansson (2002 ▶); Huang et al. (2009 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For ring conformations, see: Duax & Norton (1975 ▶). For the synthesis of the title compound, see: Shastri et al. (2004 ▶); Vasilliev & Polackov (2000 ▶).

Experimental

Crystal data

C₁₆H₁₆ClNO₂S₂
M _r = 353.87
Monoclinic,
a = 4.9427 (3) Å
b = 11.5010 (6) Å
c = 14.0006 (8) Å
β = 90.271 (6)°
V = 795.87 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.886, T _max = 1.000
13944 measured reflections
2801 independent reflections
2678 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.082
S = 1.04
2801 reflections
200 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ▶), with 1394 Friedel pairs
Flack parameter: −0.01 (10)

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/S1600536812007933/lh5420sup1.cif

e-68-0o878-sup1.cif^{(24.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007933/lh5420Isup2.hkl

e-68-0o878-Isup2.hkl^{(134.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812007933/lh5420Isup3.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
C6—H6⋯O2ⁱ	0.93	2.41	3.167 (5)	139

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Symmetry code: (i) Inline graphic .

Acknowledgments

KMK is grateful to Karnatak Science College, Dharwad, for providing laboratory facilities. RK acknowledges the Department of Science and Technology for the single-crystal X-ray diffractometer, sanctioned as a National Facility under Project No. SR/S2/CMP-47/2003.

supplementary crystallographic information

Comment

Coumarins are an important class of heterocycles, which are widespread in the plant kingdom and have been extensively reported. Coumarin derivatives with various substituents at the C-4 position have revealed potential as anti-microbial, anti-viral, anti-oxidant, anti-inflammatory and anti-cancer agents (Kulkarni et al., 2006). They have also found a place and subsequent use in laser dyes, non-linear optical chromophores, fluorescent whiteners, fluorescent probes and solar energy collectors due to their outstanding optical properties (Jones et al., 1985; Trenor et al., 2004; Hung et al., 2007). Dithiocarbamate (DTC) derivatives are valuable compounds due to their interesting chemistry and utility. These compounds have shown wide applications as pesticides, fungicides in agriculture, sulfur vulcanization and anti-cancer agents (Bergendorff & Hansson, 2002; Huang et al., 2009). In our work, we have been able to link a DTC moiety at C-4 methylene carbon and it was a thought of considerable interest to study the effect of this moiety on the total solid-state conformation of the molecule. A new series of piperidine-1-dithiocarbomate derivatives of 4-substituted coumarin was synthesized in a single step and screened for antimicrobial, anti-diabetic, DNA binding and DNA cleavage activity. In this paper we report the crystal structure of (7-Chloro-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbodithioate (I).

The molecular structure of (I) is shown in Fig. 1. The bond lengths (Allen et al., 1987) and angles in the molecule are within normal ranges. The pyridine ring adopts a normal chair conformation (asymmetry parameters: ΔC_s(C15—N1) = 0.94; ΔC₂(C16—C15) = 2.5 (Duax & Norton, 1975). The dihedral angle bewteen pyran and benzene rings in the coumarin moiety 3.5 (1)°. In the crystal, weak C—H···O hydrogen bonds link molecules along [001] (Fig. 2). In addition, π–π interactions between the pyran ring at (x, y, z) and the benzene ring at (1 + x, y, z) are present [centroid separation = 3.712 (2) Å, interplanar spacing = 3.407 Å and centroid shift = 1.47 Å].

Experimental

4-Bromomethyl coumarin required for the synthesis of the target molecule was synthesized according to an already reported procedure (Shastri et al., 2004) involving the Pechmann cyclization of phenols with 4-Bromoethyl acetoacetate and the potassium salt of piperidine-1-dithiocarbomate was synthesized according to the procedure reported (Vasilliev & Polackov, 2000).

A mixture of 2.73 g (0.01 mol) of 7-chloro-4-bromomethyl coumarin and 1.99 g (0.01 mol) of potassium salt of piperidine-1-dithiocarbomate in 30 ml dry alcohol was stirred for 12 h 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, the solvent evaporated and recrystallized 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. 407–409 K. IR (KBr): 1720 cm-1 (C═O), 1430 cm-1 (C═S), 849 cm-1 (C—N), 771 cm-1 (C—Cl). GCMS: m/e: 353.03. 1H NMR (300 MHz, CdCl3, δ, p.p.m.): 2.81 (s, 4H, C13 & C17—H), 2.79 (s, 6H, C14, C16 & C16—H), 4.72 (s, 2H, C4—CH2), 6.21 (s, 1H, C3—H), 7.18 (d, 2H, C6 & C8—H), 7.47 (d, 1H C5—H). Elemental analysis: C, 54.27; H, 4.54; Cl, 10.00; N, 3.92; O, 9.01; S, 18.09.