Crystal structure of (7-methyl-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbo-di-thio-ate.

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 carbodi-thio-ate group. In the crystal, C-H⋯O and weak C-H⋯S hydrogen bonds link the mol-ecules into chains along [001]. The crystal structure also features C-H⋯π and π-π inter-actions, with a centroid-centroid distance of 3.7097 (17) Å.

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 = 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

Δρmax = 0.14 e Å−3

Δρmin = −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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015013699/zl2626sup1.cif

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

Click here for additional data file.

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

Click here for additional data file.

. 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.

. 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

C17H19NO2S2	Dx = 1.393 Mg m−3
Mr = 333.45	Melting point: 420 K
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 4.9641 (2) Å	Cell parameters from 2119 reflections
b = 11.4351 (3) Å	θ = 1.8–25.0°
c = 14.0023 (4) Å	µ = 0.34 mm−1
β = 90.743 (2)°	T = 296 K
V = 794.77 (4) Å3	Plate, colourless
Z = 2	0.24 × 0.20 × 0.12 mm
F(000) = 352

Bruker SMART CCD area-detector diffractometer	2119 independent reflections
Radiation source: fine-focus sealed tube	2027 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
Detector resolution: 10.0 pixels mm-1	θmax = 25.0°, θmin = 1.8°
ω and φ scans	h = −5→5
Absorption correction: ψ scan (SADABS; Sheldrick, 2007)	k = −13→13
Tmin = 0.770, Tmax = 1.000	l = −13→16
4426 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.026	w = 1/[σ2(Fo2) + (0.0331P)2 + 0.0991P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.062	(Δ/σ)max < 0.001
S = 1.04	Δρmax = 0.14 e Å−3
2119 reflections	Δρmin = −0.13 e Å−3
200 parameters	Absolute structure: Flack x determined using 704 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
2 restraints	Absolute structure parameter: 0.05 (3)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
S1	0.15995 (16)	0.77643 (6)	0.48353 (6)	0.0417 (2)
S2	0.42720 (17)	0.60022 (8)	0.35570 (7)	0.0529 (3)
O3	0.1614 (4)	0.99061 (19)	0.14352 (14)	0.0405 (5)
O4	0.4912 (5)	0.8912 (2)	0.07897 (17)	0.0579 (7)
N5	0.0507 (6)	0.5536 (2)	0.4834 (2)	0.0496 (7)
C6	0.3753 (7)	0.9153 (3)	0.1512 (2)	0.0414 (8)
C7	0.4412 (7)	0.8712 (3)	0.2455 (2)	0.0379 (8)
H7	0.5761	0.8152	0.2518	0.045*
C8	0.3150 (6)	0.9079 (2)	0.3245 (2)	0.0324 (7)
C9	0.1022 (6)	0.9951 (2)	0.3146 (2)	0.0320 (7)
C10	0.0312 (6)	1.0321 (2)	0.2230 (2)	0.0331 (7)
C11	−0.1659 (6)	1.1147 (3)	0.2057 (2)	0.0373 (7)
H11	−0.2102	1.1357	0.1433	0.045*
C12	−0.2979 (6)	1.1663 (2)	0.2814 (2)	0.0370 (7)
C13	−0.2277 (6)	1.1305 (3)	0.3735 (2)	0.0396 (8)
H13	−0.3149	1.1640	0.4252	0.047*
C14	−0.5104 (7)	1.2582 (3)	0.2648 (3)	0.0509 (9)
H14A	−0.5426	1.2672	0.1975	0.076*
H14B	−0.4501	1.3312	0.2913	0.076*
H14C	−0.6742	1.2348	0.2952	0.076*
C15	−0.0339 (6)	1.0474 (2)	0.3902 (2)	0.0366 (7)
H15	0.0076	1.0254	0.4526	0.044*
C16	0.4049 (6)	0.8639 (3)	0.4206 (2)	0.0379 (7)
H16A	0.4527	0.9305	0.4601	0.045*
H16B	0.5665	0.8174	0.4125	0.045*
C17	0.2071 (6)	0.6311 (3)	0.4400 (2)	0.0378 (7)
C18	−0.1184 (8)	0.5752 (3)	0.5662 (3)	0.0561 (10)
H18A	−0.3046	0.5577	0.5499	0.067*
H18B	−0.1071	0.6570	0.5839	0.067*
C19	−0.0287 (10)	0.5001 (3)	0.6495 (3)	0.0669 (11)
H19A	0.1498	0.5243	0.6704	0.080*
H19B	−0.1507	0.5116	0.7022	0.080*
C20	−0.0229 (10)	0.3718 (3)	0.6234 (3)	0.0746 (13)
H20A	−0.2056	0.3438	0.6136	0.090*
H20B	0.0579	0.3275	0.6754	0.090*
C21	0.1378 (9)	0.3527 (3)	0.5330 (3)	0.0733 (14)
H21A	0.3265	0.3689	0.5461	0.088*
H21B	0.1224	0.2716	0.5136	0.088*
C22	0.0400 (8)	0.4302 (3)	0.4529 (3)	0.0630 (11)
H22A	0.1521	0.4192	0.3974	0.076*
H22B	−0.1436	0.4095	0.4353	0.076*

	U11	U22	U33	U12	U13	U23
S1	0.0590 (5)	0.0291 (4)	0.0373 (4)	0.0030 (4)	0.0125 (4)	0.0021 (4)
S2	0.0684 (6)	0.0435 (5)	0.0469 (5)	0.0125 (4)	0.0112 (5)	−0.0040 (4)
O3	0.0532 (14)	0.0428 (13)	0.0256 (12)	0.0032 (10)	0.0063 (10)	0.0005 (9)
O4	0.0800 (17)	0.0586 (16)	0.0356 (14)	0.0054 (14)	0.0226 (13)	−0.0038 (11)
N5	0.0614 (18)	0.0287 (13)	0.0591 (19)	0.0034 (12)	0.0108 (16)	−0.0015 (12)
C6	0.055 (2)	0.0355 (17)	0.034 (2)	−0.0090 (16)	0.0097 (17)	−0.0066 (14)
C7	0.0457 (19)	0.0311 (16)	0.0370 (19)	−0.0016 (14)	0.0064 (16)	0.0018 (13)
C8	0.0378 (17)	0.0284 (15)	0.0311 (17)	−0.0092 (13)	0.0014 (14)	0.0009 (12)
C9	0.0389 (17)	0.0287 (15)	0.0285 (18)	−0.0074 (13)	0.0054 (14)	0.0013 (12)
C10	0.0429 (17)	0.0304 (15)	0.0262 (16)	−0.0078 (13)	0.0048 (14)	−0.0022 (12)
C11	0.0458 (19)	0.0343 (16)	0.0319 (18)	−0.0061 (15)	−0.0001 (15)	0.0054 (13)
C12	0.0410 (17)	0.0295 (16)	0.0407 (19)	−0.0082 (13)	0.0063 (15)	0.0018 (14)
C13	0.0464 (19)	0.0342 (16)	0.038 (2)	−0.0052 (15)	0.0136 (16)	−0.0059 (13)
C14	0.049 (2)	0.0407 (19)	0.063 (2)	0.0030 (16)	0.0030 (19)	0.0030 (16)
C15	0.0479 (18)	0.0354 (16)	0.0266 (16)	−0.0073 (15)	0.0026 (15)	0.0009 (13)
C16	0.0450 (19)	0.0350 (16)	0.0338 (18)	−0.0026 (14)	0.0008 (15)	−0.0004 (14)
C17	0.0439 (18)	0.0316 (16)	0.0377 (19)	0.0058 (14)	−0.0067 (15)	−0.0004 (13)
C18	0.061 (2)	0.040 (2)	0.068 (3)	0.0003 (17)	0.014 (2)	0.0126 (17)
C19	0.082 (3)	0.055 (2)	0.064 (3)	−0.003 (2)	−0.001 (2)	0.0077 (19)
C20	0.085 (3)	0.048 (2)	0.090 (4)	−0.011 (2)	−0.035 (3)	0.024 (2)
C21	0.073 (3)	0.038 (2)	0.109 (4)	−0.001 (2)	−0.026 (3)	−0.002 (2)
C22	0.075 (3)	0.0324 (18)	0.081 (3)	−0.0030 (18)	0.003 (2)	−0.0062 (18)

S1—C17	1.786 (3)	C13—H13	0.9300
S1—C16	1.812 (3)	C14—H14A	0.9600
S2—C17	1.657 (3)	C14—H14B	0.9600
O3—C6	1.370 (4)	C14—H14C	0.9600
O3—C10	1.378 (3)	C15—H15	0.9300
O4—C6	1.202 (4)	C16—H16A	0.9700
N5—C17	1.330 (4)	C16—H16B	0.9700
N5—C18	1.461 (4)	C18—C19	1.511 (5)
N5—C22	1.475 (4)	C18—H18A	0.9700
C6—C7	1.447 (4)	C18—H18B	0.9700
C7—C8	1.346 (4)	C19—C20	1.512 (6)
C7—H7	0.9300	C19—H19A	0.9700
C8—C9	1.458 (4)	C19—H19B	0.9700
C8—C16	1.499 (4)	C20—C21	1.521 (6)
C9—C10	1.392 (4)	C20—H20A	0.9700
C9—C15	1.397 (4)	C20—H20B	0.9700
C10—C11	1.379 (4)	C21—C22	1.505 (6)
C11—C12	1.385 (4)	C21—H21A	0.9700
C11—H11	0.9300	C21—H21B	0.9700
C12—C13	1.394 (5)	C22—H22A	0.9700
C12—C14	1.505 (4)	C22—H22B	0.9700
C13—C15	1.371 (5)
C17—S1—C16	104.81 (15)	C8—C16—H16A	108.4
C6—O3—C10	121.6 (2)	S1—C16—H16A	108.4
C17—N5—C18	126.5 (3)	C8—C16—H16B	108.4
C17—N5—C22	121.6 (3)	S1—C16—H16B	108.4
C18—N5—C22	111.9 (3)	H16A—C16—H16B	107.5
O4—C6—O3	117.2 (3)	N5—C17—S2	125.3 (2)
O4—C6—C7	125.6 (3)	N5—C17—S1	112.6 (2)
O3—C6—C7	117.1 (3)	S2—C17—S1	122.13 (19)
C8—C7—C6	122.6 (3)	N5—C18—C19	110.5 (3)
C8—C7—H7	118.7	N5—C18—H18A	109.6
C6—C7—H7	118.7	C19—C18—H18A	109.6
C7—C8—C9	118.7 (3)	N5—C18—H18B	109.6
C7—C8—C16	119.8 (3)	C19—C18—H18B	109.6
C9—C8—C16	121.5 (3)	H18A—C18—H18B	108.1
C10—C9—C15	116.7 (3)	C20—C19—C18	111.8 (4)
C10—C9—C8	118.0 (3)	C20—C19—H19A	109.3
C15—C9—C8	125.3 (3)	C18—C19—H19A	109.3
C11—C10—O3	115.7 (3)	C20—C19—H19B	109.3
C11—C10—C9	122.7 (3)	C18—C19—H19B	109.3
O3—C10—C9	121.6 (3)	H19A—C19—H19B	107.9
C10—C11—C12	120.0 (3)	C19—C20—C21	110.6 (3)
C10—C11—H11	120.0	C19—C20—H20A	109.5
C12—C11—H11	120.0	C21—C20—H20A	109.5
C11—C12—C13	117.9 (3)	C19—C20—H20B	109.5
C11—C12—C14	121.2 (3)	C21—C20—H20B	109.5
C13—C12—C14	120.9 (3)	H20A—C20—H20B	108.1
C15—C13—C12	121.9 (3)	C22—C21—C20	111.6 (4)
C15—C13—H13	119.1	C22—C21—H21A	109.3
C12—C13—H13	119.1	C20—C21—H21A	109.3
C12—C14—H14A	109.5	C22—C21—H21B	109.3
C12—C14—H14B	109.5	C20—C21—H21B	109.3
H14A—C14—H14B	109.5	H21A—C21—H21B	108.0
C12—C14—H14C	109.5	N5—C22—C21	109.7 (3)
H14A—C14—H14C	109.5	N5—C22—H22A	109.7
H14B—C14—H14C	109.5	C21—C22—H22A	109.7
C13—C15—C9	120.9 (3)	N5—C22—H22B	109.7
C13—C15—H15	119.6	C21—C22—H22B	109.7
C9—C15—H15	119.6	H22A—C22—H22B	108.2
C8—C16—S1	115.4 (2)
C10—O3—C6—O4	−173.9 (3)	C14—C12—C13—C15	−179.7 (3)
C10—O3—C6—C7	6.4 (4)	C12—C13—C15—C9	0.1 (5)
O4—C6—C7—C8	175.3 (3)	C10—C9—C15—C13	0.2 (4)
O3—C6—C7—C8	−5.1 (4)	C8—C9—C15—C13	178.6 (3)
C6—C7—C8—C9	0.4 (4)	C7—C8—C16—S1	−115.5 (3)
C6—C7—C8—C16	−176.3 (3)	C9—C8—C16—S1	67.9 (3)
C7—C8—C9—C10	3.0 (4)	C17—S1—C16—C8	85.8 (3)
C16—C8—C9—C10	179.6 (3)	C18—N5—C17—S2	171.3 (3)
C7—C8—C9—C15	−175.4 (3)	C22—N5—C17—S2	−6.1 (5)
C16—C8—C9—C15	1.2 (4)	C18—N5—C17—S1	−7.9 (4)
C6—O3—C10—C11	174.8 (3)	C22—N5—C17—S1	174.7 (3)
C6—O3—C10—C9	−3.2 (4)	C16—S1—C17—N5	176.6 (2)
C15—C9—C10—C11	−1.0 (4)	C16—S1—C17—S2	−2.7 (2)
C8—C9—C10—C11	−179.6 (3)	C17—N5—C18—C19	−118.1 (4)
C15—C9—C10—O3	176.8 (2)	C22—N5—C18—C19	59.5 (4)
C8—C9—C10—O3	−1.7 (4)	N5—C18—C19—C20	−55.0 (5)
O3—C10—C11—C12	−176.5 (2)	C18—C19—C20—C21	51.6 (5)
C9—C10—C11—C12	1.5 (4)	C19—C20—C21—C22	−52.7 (5)
C10—C11—C12—C13	−1.1 (4)	C17—N5—C22—C21	117.6 (4)
C10—C11—C12—C14	178.9 (3)	C18—N5—C22—C21	−60.2 (4)
C11—C12—C13—C15	0.3 (4)	C20—C21—C22—N5	56.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O4i	0.93	2.45	3.223 (4)	140
C16—H16B···S2	0.97	2.70	3.152 (4)	109
C18—H18B···S1	0.97	2.38	2.930 (4)	116
C22—H22A···S2	0.97	2.55	3.065 (4)	113

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

Symmetry code: (i) .