(5,7-Dimethyl-2-oxo-2H-chromen-4-yl)methyl diethyl-dithio-carbamate.

In the title compound, C(17)H(21)NO(2)S(2), the coumarin ring system is nearly planar, with a maximum deviation of 0.080 (2) Å from the mean plane. An intra-molecular C-H⋯S hydrogen bond occurs. The crystal structure features C-H⋯S hydrogen bonds and weak π-π inter-actions with a centroid-centroid distance of 3.679 (1) Å.

Related literature

For biological applications of coumarins and dithio­carbamates, see: Smith et al. (1998 ▶); Nawrot-Modraka et al. (2006 ▶); Basanagouda et al. (2009 ▶); Kalkhambkar et al. (2007 ▶); El-Shorbagi (2000 ▶); Ronconi et al. (2006 ▶); Cvek & Dvorak (2007 ▶). For a related structure, see: Kumar et al. (2012 ▶). For the synthesis of the title compound, see: Shastri et al. (2004 ▶).

Experimental

Crystal data

C17H21NO2S2

M = 335.47

Monoclinic,

a = 7.8570 (2) Å

b = 23.7745 (5) Å

c = 9.7684 (2) Å

β = 109.483 (1)°

V = 1720.22 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.32 mm−1

T = 293 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

14939 measured reflections

3033 independent reflections

2803 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.135

S = 1.04

3033 reflections

204 parameters

H-atom parameters constrained

Δρmax = 0.90 e Å−3

Δρmin = −0.73 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: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812019757/wn2474sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019757/wn2474Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812019757/wn2474Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C17H21NO2S2	F(000) = 712
Mr = 335.47	Dx = 1.295 Mg m−3
Monoclinic, P21/n	Melting point: 409 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 7.8570 (2) Å	Cell parameters from 3033 reflections
b = 23.7745 (5) Å	θ = 1.7–25.0°
c = 9.7684 (2) Å	µ = 0.32 mm−1
β = 109.483 (1)°	T = 293 K
V = 1720.22 (7) Å3	Plate, colourless
Z = 4	0.24 × 0.20 × 0.12 mm

Bruker SMART CCD area-detector diffractometer	3033 independent reflections
Radiation source: fine-focus sealed tube	2803 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
ω and φ scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: ψ scan (SADABS; Sheldrick, 2007)	h = −9→9
Tmin = 0.770, Tmax = 1.000	k = −26→28
14939 measured reflections	l = −11→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051	H-atom parameters constrained
wR(F2) = 0.135	w = 1/[σ2(Fo2) + (0.0643P)2 + 1.5942P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.003
3033 reflections	Δρmax = 0.90 e Å−3
204 parameters	Δρmin = −0.73 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0052 (14)

Experimental. IR (KBr) 670 c m-1 (C—S), 1204 c m-1 (C=S), 1047 c m-1 (C—O), 823 c m-1 (C—N),1279 c m-1 (C—O—C), 1716 c m-1 (C=O).GCMS data m/e = 335. 1H NMR (400 MHz, CDCl3, δ, p.p.m.): 1.58 (d Ethylene-6H, CH3), 2.46 (s,3H, CH3), 2.71 (s,3H, CH3), 3.88 (s,2H, Ethylene-CH2), 4.21 (s,2H, Ethylene-CH2), 4.50 (s 2H, Methylene-CH2), 6.53 (s,1H, Ar—H), 6.92 (s,1H, Ar—H), 7.03 (s,1H, Ar—H).

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
S1	0.15831 (9)	0.15127 (3)	0.66095 (6)	0.0434 (2)
S2	0.25909 (15)	0.14818 (4)	0.38884 (10)	0.0773 (3)
O3	0.77521 (19)	0.04484 (8)	0.88072 (17)	0.0414 (4)
O4	0.8065 (3)	0.01657 (10)	0.6765 (2)	0.0610 (6)
N5	0.1516 (4)	0.23806 (10)	0.4975 (3)	0.0583 (6)
C6	0.7641 (3)	0.06546 (11)	1.1089 (2)	0.0395 (5)
H6	0.8887	0.0606	1.1437	0.047*
C7	0.6727 (3)	0.07803 (10)	1.2025 (2)	0.0401 (5)
C8	0.4863 (3)	0.08315 (10)	1.1453 (2)	0.0378 (5)
H8	0.4236	0.0902	1.2091	0.045*
C9	0.3886 (3)	0.07847 (9)	0.9997 (2)	0.0329 (5)
C10	0.4826 (3)	0.06808 (9)	0.9000 (2)	0.0294 (5)
C11	0.6692 (3)	0.06000 (9)	0.9621 (2)	0.0327 (5)
C12	0.4095 (3)	0.06440 (9)	0.7418 (2)	0.0312 (5)
C13	0.5170 (3)	0.04836 (10)	0.6673 (2)	0.0380 (5)
H13	0.4675	0.0459	0.5668	0.046*
C14	0.7056 (3)	0.03479 (11)	0.7350 (3)	0.0405 (5)
C15	0.7704 (4)	0.08551 (15)	1.3626 (3)	0.0628 (8)
H15A	0.7936	0.0493	1.4088	0.094*
H15B	0.6971	0.1074	1.4042	0.094*
H15C	0.8827	0.1046	1.3770	0.094*
C16	0.1861 (3)	0.08263 (12)	0.9590 (3)	0.0465 (6)
H16A	0.1543	0.0847	1.0456	0.070*
H16B	0.1310	0.0500	0.9041	0.070*
H16C	0.1442	0.1158	0.9016	0.070*
C17	0.2169 (3)	0.07796 (10)	0.6516 (2)	0.0369 (5)
H17A	0.1363	0.0548	0.6844	0.044*
H17B	0.1982	0.0683	0.5512	0.044*
C18	0.1913 (4)	0.18349 (11)	0.5078 (3)	0.0480 (6)
C19	0.1622 (6)	0.27172 (15)	0.3738 (4)	0.0795 (11)
H19A	0.1363	0.2478	0.2887	0.095*
H19B	0.0718	0.3012	0.3524	0.095*
C20	0.0865 (5)	0.26865 (13)	0.6014 (4)	0.0666 (9)
H20A	0.1272	0.3074	0.6075	0.080*
H20B	0.1384	0.2519	0.6968	0.080*
C21	−0.1163 (5)	0.26762 (16)	0.5582 (4)	0.0793 (10)
H21A	−0.1682	0.2849	0.4647	0.119*
H21B	−0.1529	0.2879	0.6286	0.119*
H21C	−0.1570	0.2294	0.5538	0.119*
C22	0.3417 (7)	0.29714 (19)	0.4049 (7)	0.1145 (17)
H22A	0.3700	0.3194	0.4917	0.172*
H22B	0.3420	0.3206	0.3251	0.172*
H22C	0.4303	0.2680	0.4184	0.172*

	U11	U22	U33	U12	U13	U23
S1	0.0513 (4)	0.0436 (4)	0.0340 (3)	0.0154 (3)	0.0127 (3)	0.0011 (2)
S2	0.1254 (8)	0.0562 (5)	0.0777 (6)	0.0240 (5)	0.0703 (6)	0.0081 (4)
O3	0.0260 (8)	0.0627 (11)	0.0369 (9)	0.0014 (7)	0.0124 (6)	0.0009 (8)
O4	0.0491 (11)	0.0906 (16)	0.0508 (11)	0.0181 (10)	0.0267 (9)	−0.0012 (10)
N5	0.0738 (16)	0.0432 (13)	0.0683 (16)	0.0112 (11)	0.0373 (13)	0.0056 (11)
C6	0.0270 (11)	0.0512 (14)	0.0360 (12)	−0.0054 (10)	0.0046 (9)	0.0016 (10)
C7	0.0441 (13)	0.0425 (13)	0.0300 (11)	−0.0084 (10)	0.0074 (10)	−0.0005 (9)
C8	0.0424 (13)	0.0403 (13)	0.0351 (12)	−0.0017 (10)	0.0188 (10)	−0.0017 (9)
C9	0.0311 (11)	0.0325 (11)	0.0361 (12)	0.0004 (9)	0.0126 (9)	0.0013 (9)
C10	0.0270 (10)	0.0287 (10)	0.0318 (11)	−0.0028 (8)	0.0090 (9)	0.0004 (8)
C11	0.0279 (11)	0.0383 (12)	0.0331 (11)	−0.0031 (9)	0.0117 (9)	0.0024 (9)
C12	0.0303 (11)	0.0283 (10)	0.0320 (11)	−0.0002 (8)	0.0065 (9)	0.0002 (8)
C13	0.0389 (12)	0.0439 (13)	0.0294 (11)	0.0050 (10)	0.0091 (9)	0.0002 (9)
C14	0.0389 (12)	0.0498 (14)	0.0366 (12)	0.0040 (11)	0.0177 (10)	0.0036 (10)
C15	0.0609 (18)	0.087 (2)	0.0334 (14)	−0.0135 (16)	0.0061 (12)	−0.0067 (14)
C16	0.0348 (13)	0.0618 (16)	0.0475 (14)	0.0073 (11)	0.0199 (11)	0.0059 (12)
C17	0.0332 (12)	0.0381 (12)	0.0338 (12)	0.0033 (9)	0.0035 (9)	−0.0026 (9)
C18	0.0528 (15)	0.0451 (14)	0.0500 (15)	0.0078 (11)	0.0224 (12)	0.0020 (11)
C19	0.104 (3)	0.0531 (18)	0.101 (3)	0.0124 (18)	0.060 (2)	0.0154 (18)
C20	0.097 (2)	0.0421 (15)	0.069 (2)	0.0145 (15)	0.0382 (18)	−0.0025 (14)
C21	0.094 (3)	0.072 (2)	0.086 (2)	0.0324 (19)	0.049 (2)	0.0158 (19)
C22	0.132 (4)	0.079 (3)	0.165 (5)	−0.026 (3)	0.093 (4)	−0.017 (3)

S1—C18	1.775 (3)	C13—C14	1.443 (3)
S1—C17	1.813 (2)	C13—H13	0.9300
S2—C18	1.659 (3)	C15—H15A	0.9600
O3—C14	1.365 (3)	C15—H15B	0.9600
O3—C11	1.377 (3)	C15—H15C	0.9600
O4—C14	1.202 (3)	C16—H16A	0.9600
N5—C18	1.330 (4)	C16—H16B	0.9600
N5—C20	1.472 (4)	C16—H16C	0.9600
N5—C19	1.474 (4)	C17—H17A	0.9700
C6—C7	1.371 (3)	C17—H17B	0.9700
C6—C11	1.384 (3)	C19—C22	1.469 (6)
C6—H6	0.9300	C19—H19A	0.9700
C7—C8	1.388 (3)	C19—H19B	0.9700
C7—C15	1.505 (3)	C20—C21	1.506 (5)
C8—C9	1.377 (3)	C20—H20A	0.9700
C8—H8	0.9300	C20—H20B	0.9700
C9—C10	1.426 (3)	C21—H21A	0.9600
C9—C16	1.510 (3)	C21—H21B	0.9600
C10—C11	1.400 (3)	C21—H21C	0.9600
C10—C12	1.461 (3)	C22—H22A	0.9600
C12—C13	1.341 (3)	C22—H22B	0.9600
C12—C17	1.510 (3)	C22—H22C	0.9600
C18—S1—C17	105.17 (12)	C9—C16—H16B	109.5
C14—O3—C11	122.57 (17)	H16A—C16—H16B	109.5
C18—N5—C20	123.8 (2)	C9—C16—H16C	109.5
C18—N5—C19	121.0 (2)	H16A—C16—H16C	109.5
C20—N5—C19	115.1 (2)	H16B—C16—H16C	109.5
C7—C6—C11	119.4 (2)	C12—C17—S1	113.43 (15)
C7—C6—H6	120.3	C12—C17—H17A	108.9
C11—C6—H6	120.3	S1—C17—H17A	108.9
C6—C7—C8	117.8 (2)	C12—C17—H17B	108.9
C6—C7—C15	121.3 (2)	S1—C17—H17B	108.9
C8—C7—C15	120.8 (2)	H17A—C17—H17B	107.7
C9—C8—C7	124.0 (2)	N5—C18—S2	124.2 (2)
C9—C8—H8	118.0	N5—C18—S1	112.87 (19)
C7—C8—H8	118.0	S2—C18—S1	122.90 (16)
C8—C9—C10	118.8 (2)	C22—C19—N5	111.5 (4)
C8—C9—C16	116.2 (2)	C22—C19—H19A	109.3
C10—C9—C16	124.9 (2)	N5—C19—H19A	109.3
C11—C10—C9	115.73 (19)	C22—C19—H19B	109.3
C11—C10—C12	115.79 (19)	N5—C19—H19B	109.3
C9—C10—C12	128.48 (19)	H19A—C19—H19B	108.0
O3—C11—C6	113.68 (19)	N5—C20—C21	112.2 (3)
O3—C11—C10	122.26 (19)	N5—C20—H20A	109.2
C6—C11—C10	124.0 (2)	C21—C20—H20A	109.2
C13—C12—C10	119.62 (19)	N5—C20—H20B	109.2
C13—C12—C17	115.74 (19)	C21—C20—H20B	109.2
C10—C12—C17	124.64 (19)	H20A—C20—H20B	107.9
C12—C13—C14	123.5 (2)	C20—C21—H21A	109.5
C12—C13—H13	118.3	C20—C21—H21B	109.5
C14—C13—H13	118.3	H21A—C21—H21B	109.5
O4—C14—O3	117.4 (2)	C20—C21—H21C	109.5
O4—C14—C13	127.0 (2)	H21A—C21—H21C	109.5
O3—C14—C13	115.58 (19)	H21B—C21—H21C	109.5
C7—C15—H15A	109.5	C19—C22—H22A	109.5
C7—C15—H15B	109.5	C19—C22—H22B	109.5
H15A—C15—H15B	109.5	H22A—C22—H22B	109.5
C7—C15—H15C	109.5	C19—C22—H22C	109.5
H15A—C15—H15C	109.5	H22A—C22—H22C	109.5
H15B—C15—H15C	109.5	H22B—C22—H22C	109.5
C9—C16—H16A	109.5

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···S2i	0.93	2.86	3.751 (2)	161
C16—H16C···S1	0.96	2.53	3.282 (3)	135

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯S2i	0.93	2.86	3.751 (2)	161
C16—H16C⋯S1	0.96	2.53	3.282 (3)	135

Symmetry code: (i) .