Ethyl (4-{[(di-ethyl-carbamo-thio-yl)sulfan-yl]meth-yl}-2-oxo-2H-chromen-7-yl)carbamate.

In the title compound, C18H22N2O4S2, the 2H-chromene ring system is essentially planar (r.m.s. deviation = 0.012 Å). The mol-ecular conformation is stabilized by a C-H⋯O hydrogen bond. In the crystal, N-H⋯S and C-H⋯O hydrogen bonds occur, the former enclosing an R (2) 2(22) ring motif, and lead to the formation of a two-dimensional slab-like network lying parallel to (10-1). π-π inter-actions are observed between inversion-related aromatic rings [shortest centroid-centroid distance = 3.6300 (11) Å].

Related literature

For biological applications of coumarins and di­thio­carbamates, see: Cao et al. (2005 ▶); Chen et al. (2008 ▶); Gerhauser et al. (1997 ▶); Mehta et al. (1995 ▶); Valizadeha & Shockravi (2005 ▶); Zhang et al. (2005 ▶). For a related structure with comparable bond lengths and for the synthesis, see: Kumar et al. (2012 ▶).

Experimental

Crystal data

C18H22N2O4S2

M = 394.50

Triclinic,

a = 8.0573 (3) Å

b = 9.0358 (4) Å

c = 14.2400 (6) Å

α = 74.137 (3)°

β = 87.831 (3)°

γ = 73.320 (2)°

V = 954.36 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.31 mm−1

T = 296 K

0.24 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.770, T max = 1.000

14877 measured reflections

3305 independent reflections

2808 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.101

S = 0.95

3305 reflections

235 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.17 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 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814001706/bt6958sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814001706/bt6958Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814001706/bt6958Isup3.cml

CCDC reference:

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

C18H22N2O4S2	Z = 2
Mr = 394.50	F(000) = 416
Triclinic, P1	Dx = 1.373 Mg m−3
Hall symbol: -P 1	Melting point: 445 K
a = 8.0573 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0358 (4) Å	Cell parameters from 3305 reflections
c = 14.2400 (6) Å	θ = 1.5–25.0°
α = 74.137 (3)°	µ = 0.31 mm−1
β = 87.831 (3)°	T = 296 K
γ = 73.320 (2)°	Plate, colourless
V = 954.36 (7) Å3	0.24 × 0.20 × 0.12 mm

Bruker SMART CCD area-detector diffractometer	3305 independent reflections
Radiation source: fine-focus sealed tube	2808 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
ω and φ scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −9→9
Tmin = 0.770, Tmax = 1.000	k = −10→10
14877 measured reflections	l = −16→16

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H-atom parameters constrained
S = 0.95	w = 1/[σ2(Fo2) + (0.0672P)2 + 0.1652P] where P = (Fo2 + 2Fc2)/3
3305 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.17 e Å−3

Experimental. IR (KBr, cm-1): 1000, 1152, 1227, 1422, 1501, 1695, 1720, 3265. GCMS: m/e: 384. 1H NMR (400 MHz, CDCl3, δ,. p.p.m): 7.68 (dd, 1H, Ar—H), 7.36 (d, 1H, Ar—H), 7.26 (s, 1H, Ar—H), 6.91 (s, 1H, NH), 6.46 (s, 2H, Ar—H), 4.71 (s, 2H, CH2), 4.29 (q, 2H, CH2), 4.06 (q, 2H, CH2), 3.78 (q, 2H, CH2), 1.59 (s, 3H, CH3), 1.35 (m, 6H, CH3). Mol. Formula: C18H22N2O4S2. Elemental analysis: C, 54.80; H, 5.62; N, 7.10 (calculated); C, 54.84; H, 5.58; N, 7.14 (found).

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	0.95674 (6)	0.46925 (5)	0.22606 (3)	0.04992 (16)
S2	0.60616 (6)	0.62085 (5)	0.29583 (3)	0.05289 (16)
O3	0.57157 (17)	1.67152 (13)	−0.18754 (9)	0.0517 (3)
O5	0.95552 (18)	1.08031 (13)	0.18541 (8)	0.0512 (3)
O4	0.7317 (2)	1.58432 (15)	−0.04675 (10)	0.0616 (4)
O6	1.1139 (3)	0.93665 (17)	0.31862 (11)	0.0900 (6)
N7	0.6313 (2)	1.41614 (16)	−0.10823 (10)	0.0480 (4)
H7	0.5682	1.4173	−0.1559	0.058*
N8	0.84521 (18)	0.36613 (16)	0.39956 (10)	0.0431 (3)
C9	0.4882 (4)	1.9375 (2)	−0.28981 (17)	0.0794 (7)
H9A	0.4919	2.0456	−0.2983	0.119*
H9B	0.3697	1.9354	−0.2885	0.119*
H9C	0.5431	1.8991	−0.3431	0.119*
C10	0.5810 (3)	1.8330 (2)	−0.19639 (14)	0.0562 (5)
H10A	0.7010	1.8343	−0.1967	0.067*
H10B	0.5267	1.8705	−0.1419	0.067*
C11	0.6522 (2)	1.55978 (19)	−0.10780 (12)	0.0441 (4)
C12	0.6996 (2)	1.26657 (19)	−0.04079 (11)	0.0404 (4)
C13	0.6722 (2)	1.1326 (2)	−0.06140 (12)	0.0440 (4)
H13	0.6091	1.1460	−0.1180	0.053*
C14	0.7369 (2)	0.98170 (19)	0.00062 (11)	0.0413 (4)
H14	0.7164	0.8944	−0.0143	0.050*
C15	0.8334 (2)	0.95701 (18)	0.08610 (11)	0.0381 (4)
C16	0.8600 (2)	1.09192 (19)	0.10417 (11)	0.0397 (4)
C17	0.7951 (2)	1.24599 (19)	0.04376 (11)	0.0427 (4)
H17	0.8147	1.3334	0.0591	0.051*
C18	0.9075 (2)	0.80158 (19)	0.15570 (11)	0.0399 (4)
C19	1.0006 (3)	0.7950 (2)	0.23349 (12)	0.0507 (5)
H19	1.0483	0.6956	0.2780	0.061*
C20	1.0302 (3)	0.9345 (2)	0.25129 (13)	0.0564 (5)
C21	0.8756 (3)	0.65683 (19)	0.13488 (12)	0.0466 (4)
H21A	0.9274	0.6457	0.0736	0.056*
H21B	0.7515	0.6775	0.1257	0.056*
C22	0.7977 (2)	0.47977 (18)	0.31595 (11)	0.0400 (4)
C23	1.0135 (3)	0.2415 (2)	0.41870 (15)	0.0568 (5)
H23A	1.0581	0.2235	0.3573	0.068*
H23B	0.9972	0.1417	0.4592	0.068*
C24	1.1436 (3)	0.2872 (4)	0.4689 (2)	0.0881 (8)
H24A	1.2513	0.2030	0.4798	0.132*
H24B	1.1011	0.3029	0.5304	0.132*
H24C	1.1619	0.3849	0.4285	0.132*
C25	0.7274 (2)	0.3530 (2)	0.48079 (12)	0.0513 (4)
H25A	0.6537	0.4594	0.4797	0.062*
H25B	0.7950	0.3090	0.5422	0.062*
C26	0.6168 (3)	0.2487 (3)	0.47493 (17)	0.0731 (6)
H26A	0.5419	0.2429	0.5291	0.110*
H26B	0.6893	0.1428	0.4771	0.110*
H26C	0.5480	0.2931	0.4148	0.110*

	U11	U22	U33	U12	U13	U23
S1	0.0656 (3)	0.0310 (2)	0.0483 (3)	−0.0110 (2)	0.0094 (2)	−0.00698 (18)
S2	0.0549 (3)	0.0449 (3)	0.0458 (3)	0.0002 (2)	−0.0096 (2)	−0.0051 (2)
O3	0.0703 (9)	0.0313 (6)	0.0473 (7)	−0.0103 (6)	−0.0114 (6)	−0.0034 (5)
O5	0.0787 (9)	0.0340 (6)	0.0398 (6)	−0.0181 (6)	−0.0181 (6)	−0.0036 (5)
O4	0.0918 (10)	0.0410 (7)	0.0514 (8)	−0.0213 (7)	−0.0214 (7)	−0.0062 (6)
O6	0.1509 (16)	0.0488 (8)	0.0661 (10)	−0.0303 (9)	−0.0594 (10)	0.0009 (7)
N7	0.0632 (10)	0.0345 (7)	0.0423 (8)	−0.0139 (7)	−0.0147 (7)	−0.0021 (6)
N8	0.0500 (8)	0.0322 (7)	0.0402 (7)	−0.0088 (6)	−0.0049 (6)	−0.0013 (6)
C9	0.127 (2)	0.0356 (10)	0.0623 (13)	−0.0109 (12)	−0.0103 (13)	−0.0040 (9)
C10	0.0799 (14)	0.0318 (9)	0.0540 (11)	−0.0136 (9)	−0.0023 (9)	−0.0088 (8)
C11	0.0536 (10)	0.0334 (9)	0.0388 (9)	−0.0076 (7)	−0.0026 (8)	−0.0040 (7)
C12	0.0464 (9)	0.0345 (8)	0.0364 (8)	−0.0117 (7)	−0.0014 (7)	−0.0031 (7)
C13	0.0530 (10)	0.0420 (9)	0.0367 (8)	−0.0169 (8)	−0.0083 (7)	−0.0054 (7)
C14	0.0535 (10)	0.0355 (8)	0.0382 (8)	−0.0192 (7)	−0.0010 (7)	−0.0086 (7)
C15	0.0473 (9)	0.0339 (8)	0.0323 (8)	−0.0138 (7)	0.0020 (7)	−0.0055 (6)
C16	0.0519 (10)	0.0357 (8)	0.0318 (8)	−0.0149 (7)	−0.0038 (7)	−0.0064 (6)
C17	0.0576 (11)	0.0322 (8)	0.0384 (9)	−0.0155 (7)	−0.0049 (7)	−0.0064 (7)
C18	0.0536 (10)	0.0336 (8)	0.0316 (8)	−0.0152 (7)	0.0029 (7)	−0.0045 (6)
C19	0.0743 (13)	0.0349 (9)	0.0381 (9)	−0.0152 (8)	−0.0093 (8)	−0.0011 (7)
C20	0.0847 (14)	0.0385 (9)	0.0422 (10)	−0.0184 (9)	−0.0198 (9)	−0.0014 (7)
C21	0.0703 (12)	0.0351 (9)	0.0348 (8)	−0.0203 (8)	0.0020 (8)	−0.0049 (7)
C22	0.0526 (10)	0.0294 (8)	0.0389 (8)	−0.0146 (7)	−0.0049 (7)	−0.0072 (6)
C23	0.0605 (12)	0.0352 (9)	0.0592 (11)	−0.0020 (8)	−0.0052 (9)	0.0009 (8)
C24	0.0551 (14)	0.0930 (18)	0.104 (2)	−0.0066 (13)	−0.0218 (13)	−0.0188 (15)
C25	0.0603 (12)	0.0476 (10)	0.0392 (9)	−0.0146 (9)	−0.0036 (8)	−0.0010 (7)
C26	0.0832 (16)	0.0737 (15)	0.0689 (14)	−0.0414 (13)	0.0086 (12)	−0.0107 (11)

S1—C22	1.7781 (17)	C14—C15	1.400 (2)
S1—C21	1.7920 (16)	C14—H14	0.9300
S2—C22	1.6714 (17)	C15—C16	1.387 (2)
O3—C11	1.335 (2)	C15—C18	1.454 (2)
O3—C10	1.454 (2)	C16—C17	1.383 (2)
O5—C20	1.375 (2)	C17—H17	0.9300
O5—C16	1.377 (2)	C18—C19	1.340 (3)
O4—C11	1.202 (2)	C18—C21	1.509 (2)
O6—C20	1.201 (2)	C19—C20	1.436 (3)
N7—C11	1.357 (2)	C19—H19	0.9300
N7—C12	1.398 (2)	C21—H21A	0.9700
N7—H7	0.8600	C21—H21B	0.9700
N8—C22	1.326 (2)	C23—C24	1.498 (3)
N8—C25	1.470 (2)	C23—H23A	0.9700
N8—C23	1.471 (2)	C23—H23B	0.9700
C9—C10	1.484 (3)	C24—H24A	0.9600
C9—H9A	0.9600	C24—H24B	0.9600
C9—H9B	0.9600	C24—H24C	0.9600
C9—H9C	0.9600	C25—C26	1.490 (3)
C10—H10A	0.9700	C25—H25A	0.9700
C10—H10B	0.9700	C25—H25B	0.9700
C12—C17	1.394 (2)	C26—H26A	0.9600
C12—C13	1.398 (2)	C26—H26B	0.9600
C13—C14	1.371 (2)	C26—H26C	0.9600
C13—H13	0.9300
C22—S1—C21	102.94 (8)	C19—C18—C15	118.47 (15)
C11—O3—C10	115.29 (14)	C19—C18—C21	124.04 (15)
C20—O5—C16	121.44 (13)	C15—C18—C21	117.48 (14)
C11—N7—C12	128.10 (15)	C18—C19—C20	122.95 (16)
C11—N7—H7	115.9	C18—C19—H19	118.5
C12—N7—H7	115.9	C20—C19—H19	118.5
C22—N8—C25	121.32 (14)	O6—C20—O5	116.39 (16)
C22—N8—C23	124.24 (15)	O6—C20—C19	126.28 (17)
C25—N8—C23	114.42 (14)	O5—C20—C19	117.33 (15)
C10—C9—H9A	109.5	C18—C21—S1	116.27 (12)
C10—C9—H9B	109.5	C18—C21—H21A	108.2
H9A—C9—H9B	109.5	S1—C21—H21A	108.2
C10—C9—H9C	109.5	C18—C21—H21B	108.2
H9A—C9—H9C	109.5	S1—C21—H21B	108.2
H9B—C9—H9C	109.5	H21A—C21—H21B	107.4
O3—C10—C9	107.06 (16)	N8—C22—S2	123.52 (13)
O3—C10—H10A	110.3	N8—C22—S1	113.94 (13)
C9—C10—H10A	110.3	S2—C22—S1	122.55 (9)
O3—C10—H10B	110.3	N8—C23—C24	112.18 (18)
C9—C10—H10B	110.3	N8—C23—H23A	109.2
H10A—C10—H10B	108.6	C24—C23—H23A	109.2
O4—C11—O3	124.67 (15)	N8—C23—H23B	109.2
O4—C11—N7	126.25 (15)	C24—C23—H23B	109.2
O3—C11—N7	109.07 (15)	H23A—C23—H23B	107.9
C17—C12—N7	123.04 (15)	C23—C24—H24A	109.5
C17—C12—C13	119.40 (15)	C23—C24—H24B	109.5
N7—C12—C13	117.55 (15)	H24A—C24—H24B	109.5
C14—C13—C12	120.94 (15)	C23—C24—H24C	109.5
C14—C13—H13	119.5	H24A—C24—H24C	109.5
C12—C13—H13	119.5	H24B—C24—H24C	109.5
C13—C14—C15	121.05 (15)	N8—C25—C26	111.89 (16)
C13—C14—H14	119.5	N8—C25—H25A	109.2
C15—C14—H14	119.5	C26—C25—H25A	109.2
C16—C15—C14	116.74 (14)	N8—C25—H25B	109.2
C16—C15—C18	118.47 (15)	C26—C25—H25B	109.2
C14—C15—C18	124.79 (15)	H25A—C25—H25B	107.9
O5—C16—C17	114.95 (14)	C25—C26—H26A	109.5
O5—C16—C15	121.31 (14)	C25—C26—H26B	109.5
C17—C16—C15	123.74 (15)	H26A—C26—H26B	109.5
C16—C17—C12	118.13 (15)	C25—C26—H26C	109.5
C16—C17—H17	120.9	H26A—C26—H26C	109.5
C12—C17—H17	120.9	H26B—C26—H26C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···S2i	0.86	2.63	3.4858 (17)	172
C17—H17···O4	0.93	2.28	2.876 (2)	121
C25—H25B···O6ii	0.97	2.49	3.306 (3)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7⋯S2i	0.86	2.63	3.4858 (17)	172
C17—H17⋯O4	0.93	2.28	2.876 (2)	121
C25—H25B⋯O6ii	0.97	2.49	3.306 (3)	142

Symmetry codes: (i) ; (ii) .