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

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ISSN: 2056-9890

(6-Meth­­oxy-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodi­thio­ate

aDepartment of Physics, Yuvaraja's College (Constituent College), University of Mysore, Mysore 570 005, Karnataka, India, bDepartment of Chemistry, Karnatak University's Karnatak Science College, Dharwad, Karnataka 580 001, India, and cDeapartment of Studies and Research in Chemistry, Tumkur University, Tumkur 572 103, Karnataka, India
*Correspondence e-mail: devarajegowda@yahoo.com

(Received 2 November 2012; accepted 25 December 2012; online 9 January 2013)

In the title compound, C16H17NO4S2, the 2H-chromene ring system is nearly planar, with a maximum deviation of 0.070 (1) Å, and the morpholine ring adopts a chair conformation; the bond-angle sum for its N atom is 357.9°. The dihedral angle between the the 2H-chromene ring and the best plane through the morpholine ring is 89.09 (6)°. An intra­molecular C—H⋯S hydrogen bond occurs. In the crystal, C—H⋯O hydrogen bonds generate R22(8) rings and ππ inter­actions occur between fused benzene rings of the chromene system [shortest centroid–centroid distance = 3.5487 (8) Å].

Related literature

For a related structure, background to coumarins and details of the synthesis of the title compound, see: Kumar et al. (2012[Kumar, K. M., Kour, D., Kapoor, K., Mahabaleshwaraiah, N. M., Kotresh, O., Gupta, V. K. & Kant, R. (2012). Acta Cryst. E68, o878-o879.]).

[Scheme 1]

Experimental

Crystal data
  • C16H17NO4S2

  • Mr = 351.43

  • Triclinic, [P \overline 1]

  • a = 7.0026 (5) Å

  • b = 7.9939 (6) Å

  • c = 14.8033 (11) Å

  • α = 75.433 (4)°

  • β = 86.642 (4)°

  • γ = 78.355 (4)°

  • V = 785.49 (10) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.36 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[Sheldrick, G. M. (2007). SADABS. University of Göttingen, Germany.]) Tmin = 0.770, Tmax = 1.000

  • 13583 measured reflections

  • 2725 independent reflections

  • 2482 reflections with I > 2σ(I)

  • Rint = 0.024

Refinement
  • R[F2 > 2σ(F2)] = 0.027

  • wR(F2) = 0.073

  • S = 1.06

  • 2725 reflections

  • 208 parameters

  • H-atom parameters constrained

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.15 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C14—H14⋯O6i 0.93 2.55 3.4582 (19) 166
C17—H17B⋯O3ii 0.96 2.57 3.386 (2) 143
C18—H18B⋯S2 0.97 2.55 3.1527 (14) 120
Symmetry codes: (i) -x-1, -y+1, -z+1; (ii) x, y-1, z.

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART and SAINT. 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 studies of coumarins (or 2H-chromen-2-ones) with possible biological activities (Kumar et al., 2012), we now describe the structure of (6-methoxy-2-oxo-2H-chromen-4-yl) methyl morpholine-4-carbodithioate.

The asymmetric unit of (6-methoxy-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodithioate is shown in Fig. 1. The 2H-chromene ring system (O3/C8–C16) is essentially planar, with a maximum deviation of 0.070 (1) Å for atom C8 and the morpholine ring adopts a chair conformation: the bond-angle sum for its N7 atom is 357.9 Å. The dihedral angle between the 2H-chromene (O3/C8–C16) ring and the morpholine (N7/O5/C20–C23) ring is 89.09 (6)°. In the crystal structure, (Fig. 2), intermolecular C14—H14···O6 and C17B—H17B···O3 and intramolecular C18—H18B···S2 hydrogen bonds observed and also ππ interactions between fused benzene Cg(3) (C11–C16) rings of chromene [shortest centroid–centroid distance = 3.5487 (8) Å] further stabilize the crystal packing

Related literature top

For a related structure, background to coumarins and details of 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 needles of the title compound were grown from a mixed solution of EtOH / CHCl3(V/V = 1/1) by slow evaporation at room temperature. Colour: yellowish. Yield= 84%, m.p.481 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 (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. Hydrogen atoms are shown as spheres of arbitrary radius.
[Figure 2] Fig. 2. The packing of molecules.
(6-Methoxy-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodithioate top
Crystal data top
C16H17NO4S2Z = 2
Mr = 351.43F(000) = 368
Triclinic, P1Dx = 1.486 Mg m3
Hall symbol: -P 1Melting point: 481 K
a = 7.0026 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.9939 (6) ÅCell parameters from 2725 reflections
c = 14.8033 (11) Åθ = 2.7–25.0°
α = 75.433 (4)°µ = 0.36 mm1
β = 86.642 (4)°T = 296 K
γ = 78.355 (4)°Plate, colourless
V = 785.49 (10) Å30.24 × 0.20 × 0.12 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2725 independent reflections
Radiation source: fine-focus sealed tube2482 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω and ϕ scansθmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
h = 88
Tmin = 0.770, Tmax = 1.000k = 99
13583 measured reflectionsl = 1717
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)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0403P)2 + 0.1479P]
where P = (Fo2 + 2Fc2)/3
2725 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C16H17NO4S2γ = 78.355 (4)°
Mr = 351.43V = 785.49 (10) Å3
Triclinic, P1Z = 2
a = 7.0026 (5) ÅMo Kα radiation
b = 7.9939 (6) ŵ = 0.36 mm1
c = 14.8033 (11) ÅT = 296 K
α = 75.433 (4)°0.24 × 0.20 × 0.12 mm
β = 86.642 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2725 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2007)
2482 reflections with I > 2σ(I)
Tmin = 0.770, Tmax = 1.000Rint = 0.024
13583 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0270 restraints
wR(F2) = 0.073H-atom parameters constrained
S = 1.06Δρmax = 0.21 e Å3
2725 reflectionsΔρmin = 0.15 e Å3
208 parameters
Special details top

Experimental. IR (KBr): 662 cm-1(C—S), 1233 cm-11 (C=S), 1032 cm-1(C—O), 842 cm-1 (C—N),1118 cm-1(C—O—C), 1703 cm-1(C=O). GCMS: m/e: 335. 1H NMR (400 MHz, CDCl3, \?, p.p.m.) 1.91 (m, 6H, Morpholine-CH2), 2.34 (s, 4H, Morpholine –CH2), 4.63 (d, 2H, Methylene-CH2),5.88(s, 1H, Ar—H), 6.39 (s, 1H, Ar—H), 7.08 (s, 1H, Ar—H), 7.12 (s, 1H, Ar—H). Elemental analysis for C16H17NO3S2: C, 57.21; H, 5.04; 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
S10.20243 (5)0.57411 (5)0.13634 (2)0.03769 (12)
S20.56769 (5)0.71727 (6)0.06898 (3)0.04523 (13)
O30.11086 (15)0.92127 (12)0.39849 (7)0.0387 (2)
O40.3416 (2)1.06890 (16)0.34092 (10)0.0637 (3)
O50.05206 (16)0.92565 (15)0.20255 (7)0.0481 (3)
O60.32490 (16)0.41563 (13)0.41094 (8)0.0478 (3)
N70.25269 (16)0.75947 (14)0.03248 (8)0.0338 (3)
C80.2732 (2)0.94051 (19)0.34374 (10)0.0423 (3)
C90.3469 (2)0.80463 (19)0.29565 (10)0.0391 (3)
H90.46390.80850.26270.047*
C100.2545 (2)0.67253 (17)0.29619 (9)0.0316 (3)
C110.0733 (2)0.66496 (16)0.34768 (8)0.0302 (3)
C120.0084 (2)0.79116 (16)0.39807 (9)0.0322 (3)
C130.1612 (2)0.79099 (18)0.45089 (9)0.0380 (3)
H130.20170.87580.48460.046*
C140.2691 (2)0.66436 (19)0.45309 (10)0.0396 (3)
H140.38360.66390.48820.047*
C150.2080 (2)0.53636 (17)0.40304 (9)0.0355 (3)
C160.0384 (2)0.53634 (17)0.35082 (9)0.0336 (3)
H160.00200.45080.31760.040*
C170.2599 (2)0.2748 (2)0.36796 (13)0.0518 (4)
H17A0.35390.19940.37870.078*
H17B0.13700.20860.39390.078*
H17C0.24480.32080.30200.078*
C180.3358 (2)0.53685 (18)0.24300 (9)0.0353 (3)
H18A0.32930.42060.28180.042*
H18B0.47180.54080.22800.042*
C190.34447 (19)0.69401 (16)0.04920 (9)0.0311 (3)
C200.0686 (2)0.71676 (19)0.05329 (10)0.0407 (3)
H20A0.00430.68570.00420.049*
H20B0.09620.61560.08020.049*
C210.0524 (2)0.8689 (2)0.11983 (11)0.0441 (4)
H21A0.16900.83410.13510.053*
H21B0.09230.96580.09010.053*
C220.2181 (2)0.9831 (2)0.18091 (11)0.0497 (4)
H22A0.17621.08060.15180.060*
H22B0.28641.02600.23830.060*
C230.3561 (2)0.8398 (2)0.11672 (10)0.0430 (3)
H23A0.41420.75020.14910.052*
H23B0.46000.88870.09890.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0381 (2)0.0462 (2)0.0334 (2)0.01826 (16)0.00258 (14)0.01081 (15)
S20.0298 (2)0.0622 (3)0.0451 (2)0.01602 (17)0.00144 (16)0.00997 (18)
O30.0470 (6)0.0347 (5)0.0383 (5)0.0103 (4)0.0010 (4)0.0142 (4)
O40.0665 (8)0.0560 (7)0.0859 (9)0.0322 (6)0.0105 (7)0.0352 (6)
O50.0433 (6)0.0585 (7)0.0405 (6)0.0172 (5)0.0066 (5)0.0014 (5)
O60.0432 (6)0.0412 (6)0.0627 (7)0.0158 (5)0.0115 (5)0.0164 (5)
N70.0285 (6)0.0383 (6)0.0351 (6)0.0111 (5)0.0005 (5)0.0066 (5)
C80.0440 (9)0.0426 (8)0.0438 (8)0.0140 (7)0.0039 (7)0.0118 (6)
C90.0347 (8)0.0430 (8)0.0414 (8)0.0098 (6)0.0002 (6)0.0118 (6)
C100.0328 (7)0.0316 (6)0.0278 (6)0.0024 (5)0.0047 (5)0.0045 (5)
C110.0343 (7)0.0283 (6)0.0254 (6)0.0030 (5)0.0039 (5)0.0032 (5)
C120.0397 (8)0.0283 (6)0.0274 (6)0.0052 (6)0.0052 (6)0.0044 (5)
C130.0457 (9)0.0344 (7)0.0323 (7)0.0020 (6)0.0026 (6)0.0107 (6)
C140.0400 (8)0.0397 (7)0.0356 (7)0.0049 (6)0.0065 (6)0.0067 (6)
C150.0372 (8)0.0307 (7)0.0361 (7)0.0076 (6)0.0006 (6)0.0029 (5)
C160.0397 (8)0.0279 (6)0.0331 (7)0.0042 (6)0.0001 (6)0.0090 (5)
C170.0464 (9)0.0387 (8)0.0733 (11)0.0102 (7)0.0034 (8)0.0174 (8)
C180.0342 (7)0.0351 (7)0.0344 (7)0.0033 (6)0.0012 (6)0.0072 (5)
C190.0292 (7)0.0295 (6)0.0366 (7)0.0051 (5)0.0034 (5)0.0127 (5)
C200.0337 (8)0.0456 (8)0.0436 (8)0.0170 (6)0.0039 (6)0.0041 (6)
C210.0327 (8)0.0516 (9)0.0454 (8)0.0084 (7)0.0024 (6)0.0068 (7)
C220.0481 (10)0.0533 (9)0.0456 (9)0.0225 (8)0.0038 (7)0.0023 (7)
C230.0342 (8)0.0559 (9)0.0381 (8)0.0149 (7)0.0036 (6)0.0061 (7)
Geometric parameters (Å, º) top
S1—C191.7846 (13)C13—C141.373 (2)
S1—C181.8107 (14)C13—H130.9300
S2—C191.6620 (14)C14—C151.395 (2)
O3—C81.3682 (18)C14—H140.9300
O3—C121.3792 (16)C15—C161.378 (2)
O4—C81.2083 (18)C16—H160.9300
O5—C211.4105 (19)C17—H17A0.9600
O5—C221.4136 (19)C17—H17B0.9600
O6—C151.3661 (17)C17—H17C0.9600
O6—C171.4134 (19)C18—H18A0.9700
N7—C191.3363 (17)C18—H18B0.9700
N7—C201.4662 (18)C20—C211.499 (2)
N7—C231.4733 (18)C20—H20A0.9700
C8—C91.440 (2)C20—H20B0.9700
C9—C101.344 (2)C21—H21A0.9700
C9—H90.9300C21—H21B0.9700
C10—C111.4453 (19)C22—C231.504 (2)
C10—C181.4995 (18)C22—H22A0.9700
C11—C121.3909 (19)C22—H22B0.9700
C11—C161.4028 (19)C23—H23A0.9700
C12—C131.383 (2)C23—H23B0.9700
C19—S1—C18103.85 (6)O6—C17—H17C109.5
C8—O3—C12121.50 (11)H17A—C17—H17C109.5
C21—O5—C22109.50 (12)H17B—C17—H17C109.5
C15—O6—C17117.51 (12)C10—C18—S1111.36 (9)
C19—N7—C20124.03 (11)C10—C18—H18A109.4
C19—N7—C23120.79 (12)S1—C18—H18A109.4
C20—N7—C23113.08 (11)C10—C18—H18B109.4
O4—C8—O3117.00 (14)S1—C18—H18B109.4
O4—C8—C9126.27 (15)H18A—C18—H18B108.0
O3—C8—C9116.73 (12)N7—C19—S2124.57 (10)
C10—C9—C8122.97 (14)N7—C19—S1112.68 (10)
C10—C9—H9118.5S2—C19—S1122.74 (8)
C8—C9—H9118.5N7—C20—C21111.40 (12)
C9—C10—C11118.87 (13)N7—C20—H20A109.3
C9—C10—C18120.67 (13)C21—C20—H20A109.3
C11—C10—C18120.46 (12)N7—C20—H20B109.3
C12—C11—C16118.41 (13)C21—C20—H20B109.3
C12—C11—C10117.82 (12)H20A—C20—H20B108.0
C16—C11—C10123.77 (12)O5—C21—C20111.41 (12)
O3—C12—C13116.84 (12)O5—C21—H21A109.3
O3—C12—C11121.63 (12)C20—C21—H21A109.3
C13—C12—C11121.52 (13)O5—C21—H21B109.3
C14—C13—C12119.35 (13)C20—C21—H21B109.3
C14—C13—H13120.3H21A—C21—H21B108.0
C12—C13—H13120.3O5—C22—C23112.76 (13)
C13—C14—C15120.46 (13)O5—C22—H22A109.0
C13—C14—H14119.8C23—C22—H22A109.0
C15—C14—H14119.8O5—C22—H22B109.0
O6—C15—C16124.29 (13)C23—C22—H22B109.0
O6—C15—C14115.64 (13)H22A—C22—H22B107.8
C16—C15—C14120.07 (13)N7—C23—C22110.63 (12)
C15—C16—C11120.20 (12)N7—C23—H23A109.5
C15—C16—H16119.9C22—C23—H23A109.5
C11—C16—H16119.9N7—C23—H23B109.5
O6—C17—H17A109.5C22—C23—H23B109.5
O6—C17—H17B109.5H23A—C23—H23B108.1
H17A—C17—H17B109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O6i0.932.553.4582 (19)166
C17—H17B···O3ii0.962.573.386 (2)143
C18—H18B···S20.972.553.1527 (14)120
Symmetry codes: (i) x1, y+1, z+1; (ii) x, y1, z.

Experimental details

Crystal data
Chemical formulaC16H17NO4S2
Mr351.43
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)7.0026 (5), 7.9939 (6), 14.8033 (11)
α, β, γ (°)75.433 (4), 86.642 (4), 78.355 (4)
V3)785.49 (10)
Z2
Radiation typeMo Kα
µ (mm1)0.36
Crystal size (mm)0.24 × 0.20 × 0.12
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2007)
Tmin, Tmax0.770, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
13583, 2725, 2482
Rint0.024
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.073, 1.06
No. of reflections2725
No. of parameters208
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.15

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O6i0.932.55003.4582 (19)166.00
C17—H17B···O3ii0.962.57003.386 (2)143.00
C18—H18B···S20.972.55003.1527 (14)120.00
Symmetry codes: (i) x1, y+1, z+1; (ii) x, y1, z.
 

Acknowledgements

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

References

First citationBruker (2001). SMART and SAINT. 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., Kour, D., Kapoor, K., Mahabaleshwaraiah, N. M., Kotresh, O., Gupta, V. K. & Kant, R. (2012). Acta Cryst. E68, o878–o879.  CSD CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (2007). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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