2-Oxo-2-(2-oxo-2H-chromen-3-yl)ethyl di­ethyl­dithio­carbamate

Meenakshi, T.G.; Devarajegowda, H.C.; Kumar, K.M.; Kotresh, O.; Devaru, V.B.

doi:10.1107/S1600536813021806

organic compounds

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ISSN: 2056-9890

Volume 69| Part 9| September 2013| Page o1454

doi:10.1107/S1600536813021806

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2-Oxo-2-(2-oxo-2H-chromen-3-yl)ethyl diethyldithiocarbamate

T. G. Meenakshi,^a H. C. Devarajegowda,^b ^* K. Mahesh Kumar,^c O. Kotresh ^c and Venkatesh B. Devaru ^d

^aDepartment of Physics, Y. Y. D. Govt. First Grade College, Belur 573 115, Hassan, Karnataka, India, ^bDepartment of Physics, Yuvaraja's College (Constituent College), University of Mysore, Mysore 570 005, Karnataka, India, ^cDepartment of Chemistry, Karnatak University's Karnatak Science College, Dharwad, Karnataka 580 001, India, and ^dP. G. Department of Physics, LVD College, Raichur 584 103, Karnataka, India
^*Correspondence e-mail: devarajegowda@yahoo.com

(Received 2 August 2013; accepted 5 August 2013; online 21 August 2013)

In the title compound, C₁₆H₁₇NO₃S₂, the dihedral angles between the O/C/C/S group and the 2H-chromene ring system and the thiocarbamate group are 14.46 (9) and 83.30 (9)°, respectively. The bond-angle sum at the N atom is 360.0°. One of the methyl C atoms lies above the thiocarbamate plane and one lies below it [deviations = 1.264 (3) and −1.147 (3) Å, respectively]. In the crystal, inversion dimers linked by pairs of C—H⋯O hydrogen bonds generate R₂²(10) loops. Weak aromatic π–π stacking interactions [shortest centroid–centroid distance = 3.8138 (11) Å] are also observed.

Related literature

For backgrond to chromenes, a related structure and the synthesis of the title compound, see: Kumar et al. (2012 ).

Experimental

Crystal data

C₁₆H₁₇NO₃S₂
M_r = 335.43
Orthorhombic, P b c n
a = 16.3379 (5) Å
b = 9.6445 (3) Å
c = 20.5078 (6) Å
V = 3231.43 (17) Å³
Z = 8
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: ψ scan (SADABS; Bruker, 2001 ) T_min = 0.770, T_max = 1.000
12047 measured reflections
2831 independent reflections
2129 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.090
S = 1.05
2831 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O5ⁱ	0.93	2.49	3.198 (2)	134
Symmetry code: (i) -x, -y+1, -z+1.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813021806/hb7115sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813021806/hb7115Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813021806/hb7115Isup3.cml

checkCIF report

Comment top

As part of our ongoing structural studies of chromene derivatives with possible biological activity (Kumar et al., 2012), we now describe the structure of the title compound, (I), (Fig. 1).

The 2H-chromene ring system is close to planar, with a maximum deviation of 0.031 (1) Å for atom C8. In the crystal, C9—H9···O5 hydrogen bonds (Table 1) and π-π interactions between fused benzene rings of chromene [shortest centroid–centroid distance = 3.8138 (11) Å] occur. The C—H···O hydrogen bonds generate an R₂ ²(10) loop.

Related literature top

For backgrond to chromenes, a related structure and the synthesis of the title compound, see: Kumar et al. (2012).

Experimental top

This compound was prepared according to the reported method (Kumar et al., 2012). Colourless blocks of the title compound were grown from a mixed solution of EtOH/CHCl₃ (V/V = 2/1) by slow evaporation at room temperature. Yield= 90%, m.p. 380 K.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The packing of molecule shows when view along c axis.

2-Oxo-2-(2-oxo-2H-chromen-3-yl)ethyl diethyldithiocarbamate top

Crystal data top

C₁₆H₁₇NO₃S₂	D_x = 1.379 Mg m⁻³
M_r = 335.43	Melting point: 380 K
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2831 reflections
a = 16.3379 (5) Å	θ = 2.0–25.0°
b = 9.6445 (3) Å	µ = 0.34 mm⁻¹
c = 20.5078 (6) Å	T = 296 K
V = 3231.43 (17) Å³	Block, colourless
Z = 8	0.24 × 0.20 × 0.12 mm
F(000) = 1408

Data collection top

Bruker SMART CCD diffractometer	2831 independent reflections
Radiation source: fine-focus sealed tube	2129 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: ψ scan (SADABS; Bruker, 2001)	h = −19→16
T_min = 0.770, T_max = 1.000	k = −11→11
12047 measured reflections	l = −21→23

Refinement top

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) = 0.090	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0414P)² + 0.5615P] where P = (F_o² + 2F_c²)/3
2831 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₁₇NO₃S₂	V = 3231.43 (17) Å³
M_r = 335.43	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 16.3379 (5) Å	µ = 0.34 mm⁻¹
b = 9.6445 (3) Å	T = 296 K
c = 20.5078 (6) Å	0.24 × 0.20 × 0.12 mm

Data collection top

Bruker SMART CCD diffractometer	2831 independent reflections
Absorption correction: ψ scan (SADABS; Bruker, 2001)	2129 reflections with I > 2σ(I)
T_min = 0.770, T_max = 1.000	R_int = 0.030
12047 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.05	Δρ_max = 0.21 e Å⁻³
2831 reflections	Δρ_min = −0.18 e Å⁻³
199 parameters

Special details top

Experimental. IR (KBr): 634 cm^-1 (C—S), 1266 cm^-1 (C=S), 1069 cm^-1 (C—O), 859 cm^-1 (C—N),1170 cm^-1 (C—O—C), 1696 cm^-1 (C=O), 1725 cm^-1 (Coumarin C=O). GCMS: m/e: 335. 1H NMR (400 MHz, CDCl₃, \?,. p.p.m): 1.24 (m, 3H, C₁₂), 1.35 (m, 3H, C₁), 3.80 (t, 2H, C₂),3.97(t, 2H, C₁₃), 4.80(s,2H, C₄), 7.27 (s, 1H, C₁₆), 7.37 (m, 1H, C₁₀),7.66 (s, 1H, C₁₁), 8.49(s, 1H, C₉).13 C NMR (400 MHz, CDCl3, \?,. p.p.m): 194(C₃), 191(C₅), 159(C₁₄), 155(C₁₅), 147(C₇), 134(C₆), 130(C₁₁), 125(C₉), 125(C₁₀), 118(C₈), 116(C₁₆), 50(C₄), 47(C₂),46(C₁₃), 12(C₁), 11(C₁₂).Elemental analysis for C₁₆H₁₇NO₃S₂: C, 57.22; H, 5.06; N, 4.11.

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	0.20407 (3)	0.56622 (6)	0.33761 (2)	0.05998 (19)
S2	0.11615 (3)	0.32066 (6)	0.28013 (3)	0.05692 (18)
O3	0.17542 (8)	0.09457 (14)	0.53601 (7)	0.0570 (4)
O4	0.26174 (8)	0.23027 (17)	0.48512 (7)	0.0714 (5)
O5	0.07374 (9)	0.50120 (16)	0.43332 (7)	0.0685 (4)
N6	0.13841 (10)	0.56284 (17)	0.22176 (7)	0.0501 (4)
C7	0.19123 (12)	0.2115 (2)	0.49934 (9)	0.0490 (5)
C8	0.12118 (10)	0.2984 (2)	0.48279 (8)	0.0417 (4)
C9	0.04753 (11)	0.2690 (2)	0.50922 (9)	0.0468 (5)
H9	0.0038	0.3278	0.5004	0.056*
C10	0.03396 (11)	0.1524 (2)	0.54993 (9)	0.0449 (5)
C11	0.09952 (12)	0.0653 (2)	0.56141 (9)	0.0481 (5)
C12	0.09278 (14)	−0.0535 (2)	0.59863 (11)	0.0628 (6)
H12	0.1376	−0.1114	0.6050	0.075*
C13	0.01817 (15)	−0.0843 (2)	0.62606 (11)	0.0658 (6)
H13	0.0126	−0.1631	0.6518	0.079*
C14	−0.04852 (14)	0.0007 (3)	0.61575 (11)	0.0631 (6)
H14	−0.0987	−0.0217	0.6344	0.076*
C15	−0.04160 (12)	0.1179 (2)	0.57822 (10)	0.0577 (5)
H15	−0.0869	0.1744	0.5715	0.069*
C16	0.12926 (12)	0.4194 (2)	0.43773 (9)	0.0468 (5)
C17	0.20748 (12)	0.4352 (2)	0.39882 (9)	0.0517 (5)
H17A	0.2200	0.3473	0.3782	0.062*
H17B	0.2518	0.4563	0.4287	0.062*
C18	0.14928 (10)	0.4828 (2)	0.27391 (9)	0.0445 (5)
C19	0.08964 (13)	0.5153 (3)	0.16571 (9)	0.0585 (6)
H19A	0.0624	0.5941	0.1459	0.070*
H19B	0.0478	0.4515	0.1808	0.070*
C20	0.14183 (16)	0.4445 (3)	0.11560 (11)	0.0759 (7)
H20A	0.1082	0.4155	0.0797	0.114*
H20B	0.1677	0.3650	0.1348	0.114*
H20C	0.1829	0.5077	0.1003	0.114*
C21	0.17643 (16)	0.7006 (2)	0.21421 (11)	0.0694 (7)
H21A	0.1894	0.7154	0.1686	0.083*
H21B	0.2273	0.7027	0.2385	0.083*
C22	0.1227 (2)	0.8147 (3)	0.23727 (15)	0.1102 (11)
H22A	0.1500	0.9019	0.2312	0.165*
H22B	0.1108	0.8019	0.2827	0.165*
H22C	0.0726	0.8141	0.2128	0.165*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0785 (4)	0.0517 (4)	0.0498 (3)	−0.0153 (3)	−0.0134 (3)	0.0112 (3)
S2	0.0549 (3)	0.0488 (3)	0.0670 (4)	−0.0095 (2)	0.0006 (2)	0.0070 (3)
O3	0.0494 (8)	0.0523 (9)	0.0693 (9)	0.0053 (6)	−0.0001 (7)	0.0199 (8)
O4	0.0480 (8)	0.0799 (12)	0.0864 (11)	0.0065 (8)	0.0037 (7)	0.0350 (9)
O5	0.0805 (10)	0.0611 (10)	0.0639 (9)	0.0304 (9)	0.0120 (8)	0.0156 (8)
N6	0.0563 (9)	0.0491 (11)	0.0450 (9)	−0.0060 (8)	−0.0037 (7)	0.0071 (8)
C7	0.0536 (12)	0.0485 (13)	0.0448 (10)	0.0028 (10)	−0.0023 (9)	0.0057 (10)
C8	0.0506 (11)	0.0390 (11)	0.0356 (9)	0.0048 (9)	−0.0019 (8)	−0.0038 (8)
C9	0.0534 (11)	0.0435 (12)	0.0434 (10)	0.0095 (9)	−0.0031 (9)	−0.0056 (10)
C10	0.0523 (11)	0.0425 (12)	0.0400 (10)	0.0011 (9)	0.0001 (8)	−0.0056 (9)
C11	0.0524 (11)	0.0464 (13)	0.0455 (11)	−0.0041 (10)	−0.0007 (9)	0.0004 (10)
C12	0.0667 (14)	0.0510 (14)	0.0707 (14)	−0.0007 (11)	−0.0040 (11)	0.0134 (12)
C13	0.0846 (17)	0.0540 (15)	0.0588 (13)	−0.0160 (13)	0.0022 (12)	0.0081 (12)
C14	0.0659 (14)	0.0632 (16)	0.0602 (13)	−0.0158 (13)	0.0136 (11)	−0.0075 (12)
C15	0.0561 (12)	0.0583 (14)	0.0586 (12)	−0.0002 (10)	0.0072 (10)	−0.0059 (12)
C16	0.0591 (12)	0.0428 (12)	0.0384 (10)	0.0064 (10)	−0.0055 (9)	−0.0019 (9)
C17	0.0594 (12)	0.0510 (13)	0.0445 (10)	−0.0019 (10)	−0.0054 (9)	0.0073 (10)
C18	0.0390 (9)	0.0486 (12)	0.0460 (11)	0.0000 (9)	0.0043 (8)	0.0051 (10)
C19	0.0561 (11)	0.0673 (15)	0.0522 (12)	−0.0056 (11)	−0.0109 (10)	0.0059 (12)
C20	0.0916 (17)	0.0818 (19)	0.0544 (13)	0.0017 (14)	−0.0066 (12)	−0.0065 (13)
C21	0.0908 (16)	0.0625 (16)	0.0550 (13)	−0.0156 (13)	−0.0106 (12)	0.0138 (12)
C22	0.177 (3)	0.068 (2)	0.085 (2)	0.024 (2)	−0.017 (2)	0.0027 (17)

Geometric parameters (Å, º) top

S1—C18	1.7762 (19)	C13—C14	1.380 (3)
S1—C17	1.7818 (19)	C13—H13	0.9300
S2—C18	1.660 (2)	C14—C15	1.372 (3)
O3—C11	1.374 (2)	C14—H14	0.9300
O3—C7	1.380 (2)	C15—H15	0.9300
O4—C7	1.202 (2)	C16—C17	1.514 (3)
O5—C16	1.206 (2)	C17—H17A	0.9700
N6—C18	1.331 (2)	C17—H17B	0.9700
N6—C19	1.472 (2)	C19—C20	1.500 (3)
N6—C21	1.474 (3)	C19—H19A	0.9700
C7—C8	1.459 (3)	C19—H19B	0.9700
C8—C9	1.350 (2)	C20—H20A	0.9600
C8—C16	1.494 (3)	C20—H20B	0.9600
C9—C10	1.418 (3)	C20—H20C	0.9600
C9—H9	0.9300	C21—C22	1.485 (4)
C10—C11	1.381 (3)	C21—H21A	0.9700
C10—C15	1.404 (3)	C21—H21B	0.9700
C11—C12	1.382 (3)	C22—H22A	0.9600
C12—C13	1.375 (3)	C22—H22B	0.9600
C12—H12	0.9300	C22—H22C	0.9600

C18—S1—C17	102.29 (9)	C8—C16—C17	118.65 (16)
C11—O3—C7	122.91 (15)	C16—C17—S1	114.62 (14)
C18—N6—C19	121.27 (17)	C16—C17—H17A	108.6
C18—N6—C21	123.41 (16)	S1—C17—H17A	108.6
C19—N6—C21	115.27 (16)	C16—C17—H17B	108.6
O4—C7—O3	115.77 (17)	S1—C17—H17B	108.6
O4—C7—C8	127.52 (19)	H17A—C17—H17B	107.6
O3—C7—C8	116.71 (16)	N6—C18—S2	124.38 (14)
C9—C8—C7	119.04 (18)	N6—C18—S1	113.30 (14)
C9—C8—C16	119.41 (17)	S2—C18—S1	122.31 (11)
C7—C8—C16	121.55 (16)	N6—C19—C20	111.66 (17)
C8—C9—C10	122.84 (17)	N6—C19—H19A	109.3
C8—C9—H9	118.6	C20—C19—H19A	109.3
C10—C9—H9	118.6	N6—C19—H19B	109.3
C11—C10—C15	117.86 (19)	C20—C19—H19B	109.3
C11—C10—C9	117.47 (17)	H19A—C19—H19B	107.9
C15—C10—C9	124.65 (18)	C19—C20—H20A	109.5
O3—C11—C10	120.69 (17)	C19—C20—H20B	109.5
O3—C11—C12	116.85 (18)	H20A—C20—H20B	109.5
C10—C11—C12	122.46 (19)	C19—C20—H20C	109.5
C13—C12—C11	118.4 (2)	H20A—C20—H20C	109.5
C13—C12—H12	120.8	H20B—C20—H20C	109.5
C11—C12—H12	120.8	N6—C21—C22	112.7 (2)
C12—C13—C14	120.6 (2)	N6—C21—H21A	109.1
C12—C13—H13	119.7	C22—C21—H21A	109.1
C14—C13—H13	119.7	N6—C21—H21B	109.1
C15—C14—C13	120.7 (2)	C22—C21—H21B	109.1
C15—C14—H14	119.7	H21A—C21—H21B	107.8
C13—C14—H14	119.7	C21—C22—H22A	109.5
C14—C15—C10	120.0 (2)	C21—C22—H22B	109.5
C14—C15—H15	120.0	H22A—C22—H22B	109.5
C10—C15—H15	120.0	C21—C22—H22C	109.5
O5—C16—C8	119.41 (18)	H22A—C22—H22C	109.5
O5—C16—C17	121.94 (18)	H22B—C22—H22C	109.5

C11—O3—C7—O4	173.66 (18)	C13—C14—C15—C10	−0.1 (3)
C11—O3—C7—C8	−5.8 (3)	C11—C10—C15—C14	−0.1 (3)
O4—C7—C8—C9	−172.6 (2)	C9—C10—C15—C14	178.54 (19)
O3—C7—C8—C9	6.8 (3)	C9—C8—C16—O5	11.3 (3)
O4—C7—C8—C16	6.9 (3)	C7—C8—C16—O5	−168.29 (18)
O3—C7—C8—C16	−173.64 (15)	C9—C8—C16—C17	−168.69 (17)
C7—C8—C9—C10	−3.5 (3)	C7—C8—C16—C17	11.7 (3)
C16—C8—C9—C10	176.94 (17)	O5—C16—C17—S1	−9.5 (3)
C8—C9—C10—C11	−1.1 (3)	C8—C16—C17—S1	170.48 (13)
C8—C9—C10—C15	−179.82 (18)	C18—S1—C17—C16	−78.83 (16)
C7—O3—C11—C10	1.4 (3)	C19—N6—C18—S2	4.5 (3)
C7—O3—C11—C12	−178.37 (18)	C21—N6—C18—S2	−172.67 (17)
C15—C10—C11—O3	−178.91 (17)	C19—N6—C18—S1	−175.84 (14)
C9—C10—C11—O3	2.3 (3)	C21—N6—C18—S1	7.0 (2)
C15—C10—C11—C12	0.8 (3)	C17—S1—C18—N6	179.60 (14)
C9—C10—C11—C12	−177.98 (19)	C17—S1—C18—S2	−0.70 (14)
O3—C11—C12—C13	178.51 (18)	C18—N6—C19—C20	−91.4 (2)
C10—C11—C12—C13	−1.2 (3)	C21—N6—C19—C20	86.0 (2)
C11—C12—C13—C14	1.0 (3)	C18—N6—C21—C22	−93.0 (2)
C12—C13—C14—C15	−0.3 (3)	C19—N6—C21—C22	89.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O5ⁱ	0.93	2.49	3.198 (2)	134

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O5ⁱ	0.93	2.49	3.198 (2)	134

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

The authors thank the Universities Sophisticated Instrumental Centre, Karnatak University, Dharwad, for the X-ray data collection and the GCMS, IR, CHNS and NMR data. KMK thanks Karnatak Science College, Dharwad, for providing laboratory facilities.

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