(IUCr) Crystallography Journals Online

Abstract top

In the title compound, C₁₇H₂₁NO₂S₂, the coumarin ring system is nearly planar, with a maximum deviation of 0.080 (2) Å from the mean plane. An intramolecular C-HS hydrogen bond occurs. The crystal structure features C-HS hydrogen bonds and weak [pi] - [pi] interactions with a centroid-centroid distance of 3.679 (1) Å.

Comment top

Coumarins constitute a class of compounds which are found widely in nature and possess diverse biological activities. Over recent decades, medicinal chemists have paid great attention to the isolation, screening and structural modifications of new coumarins. They have been found to exhibit a wide range of applications in cancer, the HIV drug development arena (Smith et al., 1998), anti-tumor, anti-bacterial and cytotoxic activity (Nawrot-Modraka et al., 2006). In 4-substituted coumarins, the groups attached at the C-4 methylene carbon been shown to influence their solid state conformations, as observed in 4-aryloxymethyl (Basanagouda et al., 2009) and 4-arylaminomethyl coumarins (Kalkhambkar et al., 2007).

Dithiocarbamates have shown wide applications as pesticides,fungicides in agriculture (El-Shorbagi, 2000), potent anticancer agents (Ronconi et al., 2006), organic intermediates, rubber additives, additives of polluted water and vulcanizing agents (Cvek & Dvorak, 2007).

In view of the above observations,we proposed that 4-substituted coumarins bearing the dithiocarbamate (DTC)group should display some interesting biological activity and the title compound was screened for fungicidal, bacterial and DNA cleavage properties.The crystal structure of a coumarin derivative linked to the DTC group has been reported (Kumar et al., 2012).

The title compound is one of a series of dithiocarbamate coumarins with potential as possible anti-microbial agents. For these reasons, in continuation of our interest in the crystal structures of coumarin derivatives, we report here its crystal structure.

The asymmetric unit of 5,7-dimethyl-2-oxo-2H-chromen-4-yl)methyl diethyldithiocarbamate is shown in Fig. 1.The coumarin ring system (O3/C6–C14) is nearly planar, with a maximum deviation from the mean plane of 0.080 (2) Å for atom C12.

In the crystal structure (Fig. 2), the molecules are connected via weak intramolecular C8—H8···S2 and intermolecular C16—H16C···S1 hydrogen bonds (Table 1). Furthermore, the crystal structure features π-π stacking interactions between the pyran ring (O3/C10–C14; centroid Cg1) and the benzene ring (C6–C11; centroid Cg2), with a Cg1···Cg2 distance of 3.679 (1) Å.

(5,7-Dimethyl-2-oxo-2H-chromen-4-yl)methyl diethyldithiocarbamate top

Crystal data top

C₁₇H₂₁NO₂S₂	F(000) = 712
M_r = 335.47	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0643P)² + 1.5942P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.003
3033 reflections	Δρ_max = 0.90 e Å⁻³
204 parameters	Δρ_min = −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)

Crystal data top

C₁₇H₂₁NO₂S₂	V = 1720.22 (7) Å³
M_r = 335.47	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.8570 (2) Å	µ = 0.32 mm⁻¹
b = 23.7745 (5) Å	T = 293 K
c = 9.7684 (2) Å	0.24 × 0.20 × 0.12 mm
β = 109.483 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3033 independent reflections
Absorption correction: ψ scan (SADABS; Sheldrick, 2007)	2803 reflections with I > 2σ(I)
T_min = 0.770, T_max = 1.000	R_int = 0.020
14939 measured reflections	θ_max = 25.0°

Refinement top

R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.135	Δρ_max = 0.90 e Å⁻³
S = 1.04	Δρ_min = −0.73 e Å⁻³
3033 reflections	Absolute structure: ?
204 parameters	Flack parameter: ?
0 restraints	Rogers parameter: ?

Special details top

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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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) x, y, z+1.

Hydrogen-bond geometry (Å, º) top

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) x, y, z+1.

supplementary materials

(5,7-Dimethyl-2-oxo-2H-chromen-4-yl)methyl diethyldithiocarbamate

K. M. Kumar, H. C. Devarajegowda, S. Jeyaseelan, N. M. Mahabaleshwaraiah and O. Kotresh

	Fig. 1. 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. The dashed line indicates the intramolecular hydrogen bond.
	Fig. 2. The packing of the molecules in the crystal structure.