organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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 ππ 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[Kumar, K. M., Devarajegowda, H. C., Jeyaseelan, S., Mahabaleshwaraiah, N. M. & Kotresh, O. (2012). Acta Cryst. E68, o1657.]).

[Scheme 1]

Experimental

Crystal data
  • C16H17NO3S2

  • Mr = 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[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.]) Tmin = 0.770, Tmax = 1.000

  • 12047 measured reflections

  • 2831 independent reflections

  • 2129 reflections with I > 2σ(I)

  • Rint = 0.030

Refinement
  • R[F2 > 2σ(F2)] = 0.035

  • wR(F2) = 0.090

  • S = 1.05

  • 2831 reflections

  • 199 parameters

  • H-atom parameters constrained

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]); software used to prepare material for publication: SHELXL97.

Supporting information


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.

Refinement top

All H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H, C—H = 0.97 Å for methylene H and C—H = 0.96 Å for methyl H,and refined using a riding model with Uiso(H) = 1.5Ueq(C) for methyl H and Uiso(H) = 1.2Ueq(C) for all other H.

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
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] 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
C16H17NO3S2Dx = 1.379 Mg m3
Mr = 335.43Melting point: 380 K
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 2831 reflections
a = 16.3379 (5) Åθ = 2.0–25.0°
b = 9.6445 (3) ŵ = 0.34 mm1
c = 20.5078 (6) ÅT = 296 K
V = 3231.43 (17) Å3Block, colourless
Z = 80.24 × 0.20 × 0.12 mm
F(000) = 1408
Data collection top
Bruker SMART CCD
diffractometer
2831 independent reflections
Radiation source: fine-focus sealed tube2129 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
ω and ϕ scansθmax = 25.0°, θmin = 2.0°
Absorption correction: ψ scan
(SADABS; Bruker, 2001)
h = 1916
Tmin = 0.770, Tmax = 1.000k = 1111
12047 measured reflectionsl = 2123
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0414P)2 + 0.5615P]
where P = (Fo2 + 2Fc2)/3
2831 reflections(Δ/σ)max = 0.001
199 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C16H17NO3S2V = 3231.43 (17) Å3
Mr = 335.43Z = 8
Orthorhombic, PbcnMo Kα radiation
a = 16.3379 (5) ŵ = 0.34 mm1
b = 9.6445 (3) ÅT = 296 K
c = 20.5078 (6) Å0.24 × 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)
Tmin = 0.770, Tmax = 1.000Rint = 0.030
12047 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.090H-atom parameters constrained
S = 1.05Δρmax = 0.21 e Å3
2831 reflectionsΔρmin = 0.18 e Å3
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
xyzUiso*/Ueq
S10.20407 (3)0.56622 (6)0.33761 (2)0.05998 (19)
S20.11615 (3)0.32066 (6)0.28013 (3)0.05692 (18)
O30.17542 (8)0.09457 (14)0.53601 (7)0.0570 (4)
O40.26174 (8)0.23027 (17)0.48512 (7)0.0714 (5)
O50.07374 (9)0.50120 (16)0.43332 (7)0.0685 (4)
N60.13841 (10)0.56284 (17)0.22176 (7)0.0501 (4)
C70.19123 (12)0.2115 (2)0.49934 (9)0.0490 (5)
C80.12118 (10)0.2984 (2)0.48279 (8)0.0417 (4)
C90.04753 (11)0.2690 (2)0.50922 (9)0.0468 (5)
H90.00380.32780.50040.056*
C100.03396 (11)0.1524 (2)0.54993 (9)0.0449 (5)
C110.09952 (12)0.0653 (2)0.56141 (9)0.0481 (5)
C120.09278 (14)0.0535 (2)0.59863 (11)0.0628 (6)
H120.13760.11140.60500.075*
C130.01817 (15)0.0843 (2)0.62606 (11)0.0658 (6)
H130.01260.16310.65180.079*
C140.04852 (14)0.0007 (3)0.61575 (11)0.0631 (6)
H140.09870.02170.63440.076*
C150.04160 (12)0.1179 (2)0.57822 (10)0.0577 (5)
H150.08690.17440.57150.069*
C160.12926 (12)0.4194 (2)0.43773 (9)0.0468 (5)
C170.20748 (12)0.4352 (2)0.39882 (9)0.0517 (5)
H17A0.22000.34730.37820.062*
H17B0.25180.45630.42870.062*
C180.14928 (10)0.4828 (2)0.27391 (9)0.0445 (5)
C190.08964 (13)0.5153 (3)0.16571 (9)0.0585 (6)
H19A0.06240.59410.14590.070*
H19B0.04780.45150.18080.070*
C200.14183 (16)0.4445 (3)0.11560 (11)0.0759 (7)
H20A0.10820.41550.07970.114*
H20B0.16770.36500.13480.114*
H20C0.18290.50770.10030.114*
C210.17643 (16)0.7006 (2)0.21421 (11)0.0694 (7)
H21A0.18940.71540.16860.083*
H21B0.22730.70270.23850.083*
C220.1227 (2)0.8147 (3)0.23727 (15)0.1102 (11)
H22A0.15000.90190.23120.165*
H22B0.11080.80190.28270.165*
H22C0.07260.81410.21280.165*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0785 (4)0.0517 (4)0.0498 (3)0.0153 (3)0.0134 (3)0.0112 (3)
S20.0549 (3)0.0488 (3)0.0670 (4)0.0095 (2)0.0006 (2)0.0070 (3)
O30.0494 (8)0.0523 (9)0.0693 (9)0.0053 (6)0.0001 (7)0.0199 (8)
O40.0480 (8)0.0799 (12)0.0864 (11)0.0065 (8)0.0037 (7)0.0350 (9)
O50.0805 (10)0.0611 (10)0.0639 (9)0.0304 (9)0.0120 (8)0.0156 (8)
N60.0563 (9)0.0491 (11)0.0450 (9)0.0060 (8)0.0037 (7)0.0071 (8)
C70.0536 (12)0.0485 (13)0.0448 (10)0.0028 (10)0.0023 (9)0.0057 (10)
C80.0506 (11)0.0390 (11)0.0356 (9)0.0048 (9)0.0019 (8)0.0038 (8)
C90.0534 (11)0.0435 (12)0.0434 (10)0.0095 (9)0.0031 (9)0.0056 (10)
C100.0523 (11)0.0425 (12)0.0400 (10)0.0011 (9)0.0001 (8)0.0056 (9)
C110.0524 (11)0.0464 (13)0.0455 (11)0.0041 (10)0.0007 (9)0.0004 (10)
C120.0667 (14)0.0510 (14)0.0707 (14)0.0007 (11)0.0040 (11)0.0134 (12)
C130.0846 (17)0.0540 (15)0.0588 (13)0.0160 (13)0.0022 (12)0.0081 (12)
C140.0659 (14)0.0632 (16)0.0602 (13)0.0158 (13)0.0136 (11)0.0075 (12)
C150.0561 (12)0.0583 (14)0.0586 (12)0.0002 (10)0.0072 (10)0.0059 (12)
C160.0591 (12)0.0428 (12)0.0384 (10)0.0064 (10)0.0055 (9)0.0019 (9)
C170.0594 (12)0.0510 (13)0.0445 (10)0.0019 (10)0.0054 (9)0.0073 (10)
C180.0390 (9)0.0486 (12)0.0460 (11)0.0000 (9)0.0043 (8)0.0051 (10)
C190.0561 (11)0.0673 (15)0.0522 (12)0.0056 (11)0.0109 (10)0.0059 (12)
C200.0916 (17)0.0818 (19)0.0544 (13)0.0017 (14)0.0066 (12)0.0065 (13)
C210.0908 (16)0.0625 (16)0.0550 (13)0.0156 (13)0.0106 (12)0.0138 (12)
C220.177 (3)0.068 (2)0.085 (2)0.024 (2)0.017 (2)0.0027 (17)
Geometric parameters (Å, º) top
S1—C181.7762 (19)C13—C141.380 (3)
S1—C171.7818 (19)C13—H130.9300
S2—C181.660 (2)C14—C151.372 (3)
O3—C111.374 (2)C14—H140.9300
O3—C71.380 (2)C15—H150.9300
O4—C71.202 (2)C16—C171.514 (3)
O5—C161.206 (2)C17—H17A0.9700
N6—C181.331 (2)C17—H17B0.9700
N6—C191.472 (2)C19—C201.500 (3)
N6—C211.474 (3)C19—H19A0.9700
C7—C81.459 (3)C19—H19B0.9700
C8—C91.350 (2)C20—H20A0.9600
C8—C161.494 (3)C20—H20B0.9600
C9—C101.418 (3)C20—H20C0.9600
C9—H90.9300C21—C221.485 (4)
C10—C111.381 (3)C21—H21A0.9700
C10—C151.404 (3)C21—H21B0.9700
C11—C121.382 (3)C22—H22A0.9600
C12—C131.375 (3)C22—H22B0.9600
C12—H120.9300C22—H22C0.9600
C18—S1—C17102.29 (9)C8—C16—C17118.65 (16)
C11—O3—C7122.91 (15)C16—C17—S1114.62 (14)
C18—N6—C19121.27 (17)C16—C17—H17A108.6
C18—N6—C21123.41 (16)S1—C17—H17A108.6
C19—N6—C21115.27 (16)C16—C17—H17B108.6
O4—C7—O3115.77 (17)S1—C17—H17B108.6
O4—C7—C8127.52 (19)H17A—C17—H17B107.6
O3—C7—C8116.71 (16)N6—C18—S2124.38 (14)
C9—C8—C7119.04 (18)N6—C18—S1113.30 (14)
C9—C8—C16119.41 (17)S2—C18—S1122.31 (11)
C7—C8—C16121.55 (16)N6—C19—C20111.66 (17)
C8—C9—C10122.84 (17)N6—C19—H19A109.3
C8—C9—H9118.6C20—C19—H19A109.3
C10—C9—H9118.6N6—C19—H19B109.3
C11—C10—C15117.86 (19)C20—C19—H19B109.3
C11—C10—C9117.47 (17)H19A—C19—H19B107.9
C15—C10—C9124.65 (18)C19—C20—H20A109.5
O3—C11—C10120.69 (17)C19—C20—H20B109.5
O3—C11—C12116.85 (18)H20A—C20—H20B109.5
C10—C11—C12122.46 (19)C19—C20—H20C109.5
C13—C12—C11118.4 (2)H20A—C20—H20C109.5
C13—C12—H12120.8H20B—C20—H20C109.5
C11—C12—H12120.8N6—C21—C22112.7 (2)
C12—C13—C14120.6 (2)N6—C21—H21A109.1
C12—C13—H13119.7C22—C21—H21A109.1
C14—C13—H13119.7N6—C21—H21B109.1
C15—C14—C13120.7 (2)C22—C21—H21B109.1
C15—C14—H14119.7H21A—C21—H21B107.8
C13—C14—H14119.7C21—C22—H22A109.5
C14—C15—C10120.0 (2)C21—C22—H22B109.5
C14—C15—H15120.0H22A—C22—H22B109.5
C10—C15—H15120.0C21—C22—H22C109.5
O5—C16—C8119.41 (18)H22A—C22—H22C109.5
O5—C16—C17121.94 (18)H22B—C22—H22C109.5
C11—O3—C7—O4173.66 (18)C13—C14—C15—C100.1 (3)
C11—O3—C7—C85.8 (3)C11—C10—C15—C140.1 (3)
O4—C7—C8—C9172.6 (2)C9—C10—C15—C14178.54 (19)
O3—C7—C8—C96.8 (3)C9—C8—C16—O511.3 (3)
O4—C7—C8—C166.9 (3)C7—C8—C16—O5168.29 (18)
O3—C7—C8—C16173.64 (15)C9—C8—C16—C17168.69 (17)
C7—C8—C9—C103.5 (3)C7—C8—C16—C1711.7 (3)
C16—C8—C9—C10176.94 (17)O5—C16—C17—S19.5 (3)
C8—C9—C10—C111.1 (3)C8—C16—C17—S1170.48 (13)
C8—C9—C10—C15179.82 (18)C18—S1—C17—C1678.83 (16)
C7—O3—C11—C101.4 (3)C19—N6—C18—S24.5 (3)
C7—O3—C11—C12178.37 (18)C21—N6—C18—S2172.67 (17)
C15—C10—C11—O3178.91 (17)C19—N6—C18—S1175.84 (14)
C9—C10—C11—O32.3 (3)C21—N6—C18—S17.0 (2)
C15—C10—C11—C120.8 (3)C17—S1—C18—N6179.60 (14)
C9—C10—C11—C12177.98 (19)C17—S1—C18—S20.70 (14)
O3—C11—C12—C13178.51 (18)C18—N6—C19—C2091.4 (2)
C10—C11—C12—C131.2 (3)C21—N6—C19—C2086.0 (2)
C11—C12—C13—C141.0 (3)C18—N6—C21—C2293.0 (2)
C12—C13—C14—C150.3 (3)C19—N6—C21—C2289.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O5i0.932.493.198 (2)134
Symmetry code: (i) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9···O5i0.932.493.198 (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.

References

First citationBruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison,Wisconsin, USA.
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals
First citationKumar, K. M., Devarajegowda, H. C., Jeyaseelan, S., Mahabaleshwaraiah, N. M. & Kotresh, O. (2012). Acta Cryst. E68, o1657.  CSD CrossRef IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds