Crystal structure of (7-methyl-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbo­di­thio­ate

K R Roopashree; T G Meenakshi; K Mahesh Kumar; O Kotresh; H C Devarajegowda

doi:10.1107/S2056989015013699

. 2015 Jul 29;71(Pt 8):o606–o607. doi: 10.1107/S2056989015013699

Crystal structure of (7-methyl-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbodithioate

K R Roopashree ^a, T G Meenakshi ^b, K Mahesh Kumar ^c, O Kotresh ^c, H C Devarajegowda ^a,^*

PMCID: PMC4571421 PMID: 26396821

Abstract

In the title compound, C₁₇H₁₉NO₂S₂, the 2H-chromene ring system is nearly planar, with a maximum deviation of 0.0383 (28) Å, and the piperidine ring adopts a chair conformation. The 2H-chromene ring makes dihedral angles of 32.89 (16) and 67.33 (8)°, respectively, with the mean planes of the piperidine ring and the carbodithioate group. In the crystal, C—H⋯O and weak C—H⋯S hydrogen bonds link the molecules into chains along [001]. The crystal structure also features C—H⋯π and π–π interactions, with a centroid–centroid distance of 3.7097 (17) Å.

Keywords: crystal structure, 2H-chromene, hydrogen bonding, C—H⋯π interactions, π–π interactions

Related literature

For biological applications of coumarins, see: Stiefel et al. (1995 ▸); Murray et al. (1982 ▸); Khan et al. (2004 ▸); Kawaii et al. (2001 ▸); Yu et al. (2003 ▸). For biological applications of dithiacarbamates, see: D’hooghe & de Kime (2006 ▸); Thorn & Ludwig (1962 ▸); Cao et al. (2005 ▸). For a related structure, see: Kumar et al. (2013 ▸).

Experimental

Crystal data

C₁₇H₁₉NO₂S₂
M _r = 333.45
Monoclinic,
a = 4.9641 (2) Å
b = 11.4351 (3) Å
c = 14.0023 (4) Å
β = 90.743 (2)°
V = 794.77 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.34 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
4426 measured reflections
2119 independent reflections
2027 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.026
wR(F ²) = 0.062
S = 1.04
2119 reflections
200 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.13 e Å⁻³
Absolute structure: Flack x determined using 704 quotients [(I ⁺)−(I ⁻)]/[(I ⁺)+(I ⁻)] (Parsons et al., 2013 ▸)
Absolute structure parameter: 0.05 (3)

Data collection: SMART (Bruker, 2001 ▸); cell refinement: SAINT (Bruker, 2001 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS2014 (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/S2056989015013699/zl2626sup1.cif

e-71-0o606-sup1.cif^{(157.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015013699/zl2626Isup2.hkl

e-71-0o606-Isup2.hkl^{(170KB, hkl)}

Click here for additional data file.^{(6.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015013699/zl2626Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015013699/zl2626fig1.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.^{(1.9MB, tif)}

. DOI: 10.1107/S2056989015013699/zl2626fig2.tif

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

CCDC reference: 1413856

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C13H13O4ⁱ	0.93	2.45	3.223(4)	140
C16H16BS2	0.97	2.70	3.152(4)	109
C18H18BS1	0.97	2.38	2.930(4)	116
C22H22AS2	0.97	2.55	3.065(4)	113

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

S1. Comment

Coumarins and their derivatives play an important role in the agricultural and pharmaceutical industries (Stiefel et al., 1995). They are widely present in higher plants such as Rutaceae, Apiaceae, Asteraceae, Leguminosae, Thymelaeaceae, and they also occur as animal and microbial metabolites (Murray et al., 1982). Most of them show a wide spectrum of pharmacological effects, including antimicrobial (Khan et al., 2004), anti-arrhythmic, antiosteoporosis, anti-HIV, and antitumor activities (Kawaii et al., 2001; Yu et al., 2003). Accordingly, many reports have described various structures and biological evaluations of numerous coumarin analogs newly synthesized or isolated from plants.

Sulfur containing molecules are currently under study as chemoprotectants in chemotherapy. Organic substances with a dithio functional group have been widely used in industry as rodent repellents, vulcanization additives in rubber manufacturing, additives in lubricants, and in agriculture as fungicides on almond trees, stone fruits, and vegetables. Among the various sulfur ligands being examined currently, dithiocarbamates have a special significance owing to their many uses, e.g. in analytical determinations, as arrestors of human immunodeficiency virus infections such as AIDS, in pharmaceutical products, in agriculture as pesticides and fungicides, and as high-pressure lubricants (D'hooghe & de Kime, 2006; Thorn & Ludwig, 1962; Cao et al., 2005). One molecule of (7-methyl-2-oxo-2H-chromen-4-yl)methylpiperidine-1-carbodithioate is shown in Fig. 1. The 2Hchromene ring system (O3/C6–C13/C15) is essentially planar, with a maximum deviation of 0.0383 (28) Å for atom C10 and the piperidine (N5/C18–C22) ring adopts a chair conformation. The dihedral angle of the 2H-chromene (O3/C6–C13/C15) ring with the piperidine (N5/C18–C22) ring and carbodithioate group are 32.89 (16)° and 67.33 (8)°, respectively. In addition, intermolecular C—H···O and weak C—H···S hydrogen bonds (Table 1) link the components into chains along [001]. The crystal structure also features C—H···π [C_g(3) (C9–C15)] and [C_g(1) (O3/C6–C10)]π–π [C_g(3) (C9–C15)] interactions, with centroid–centroid distances of 3.7081 (15) Å that further stabilize the crystal packing, Figure 2.

S2. Experimental

The title compound compound was prepared according to a reported method (Kumar et al., 2013). Colourless needles of the title compound were grown from a mixed solution of EtOH/CHCl₃ (v/v = 1/1) by slow evaporation at room temperature. Yield: 80%, m.p. 420 K.