organic compounds
(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
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 π–π interactions occur between fused benzene rings of the chromene system [shortest centroid–centroid distance = 3.5487 (8) Å].
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2001); cell 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
10.1107/S1600536812051847/gw2129sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812051847/gw2129Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812051847/gw2129Isup3.cml
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.
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.
Data collection: SMART (Bruker, 2001); cell
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).C16H17NO4S2 | Z = 2 |
Mr = 351.43 | F(000) = 368 |
Triclinic, P1 | Dx = 1.486 Mg m−3 |
Hall symbol: -P 1 | Melting point: 481 K |
a = 7.0026 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.9939 (6) Å | Cell parameters from 2725 reflections |
c = 14.8033 (11) Å | θ = 2.7–25.0° |
α = 75.433 (4)° | µ = 0.36 mm−1 |
β = 86.642 (4)° | T = 296 K |
γ = 78.355 (4)° | Plate, colourless |
V = 785.49 (10) Å3 | 0.24 × 0.20 × 0.12 mm |
Bruker SMART CCD area-detector diffractometer | 2725 independent reflections |
Radiation source: fine-focus sealed tube | 2482 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω and ϕ scans | θmax = 25.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | h = −8→8 |
Tmin = 0.770, Tmax = 1.000 | k = −9→9 |
13583 measured reflections | l = −17→17 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-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 parameters | Δρmax = 0.21 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
C16H17NO4S2 | γ = 78.355 (4)° |
Mr = 351.43 | V = 785.49 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.0026 (5) Å | Mo Kα radiation |
b = 7.9939 (6) Å | µ = 0.36 mm−1 |
c = 14.8033 (11) Å | T = 296 K |
α = 75.433 (4)° | 0.24 × 0.20 × 0.12 mm |
β = 86.642 (4)° |
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 = 1.000 | Rint = 0.024 |
13583 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.21 e Å−3 |
2725 reflections | Δρmin = −0.15 e Å−3 |
208 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.20243 (5) | 0.57411 (5) | 0.13634 (2) | 0.03769 (12) | |
S2 | 0.56769 (5) | 0.71727 (6) | 0.06898 (3) | 0.04523 (13) | |
O3 | 0.11086 (15) | 0.92127 (12) | 0.39849 (7) | 0.0387 (2) | |
O4 | 0.3416 (2) | 1.06890 (16) | 0.34092 (10) | 0.0637 (3) | |
O5 | 0.05206 (16) | 0.92565 (15) | −0.20255 (7) | 0.0481 (3) | |
O6 | −0.32490 (16) | 0.41563 (13) | 0.41094 (8) | 0.0478 (3) | |
N7 | 0.25269 (16) | 0.75947 (14) | −0.03248 (8) | 0.0338 (3) | |
C8 | 0.2732 (2) | 0.94051 (19) | 0.34374 (10) | 0.0423 (3) | |
C9 | 0.3469 (2) | 0.80463 (19) | 0.29565 (10) | 0.0391 (3) | |
H9 | 0.4639 | 0.8085 | 0.2627 | 0.047* | |
C10 | 0.2545 (2) | 0.67253 (17) | 0.29619 (9) | 0.0316 (3) | |
C11 | 0.0733 (2) | 0.66496 (16) | 0.34768 (8) | 0.0302 (3) | |
C12 | 0.0084 (2) | 0.79116 (16) | 0.39807 (9) | 0.0322 (3) | |
C13 | −0.1612 (2) | 0.79099 (18) | 0.45089 (9) | 0.0380 (3) | |
H13 | −0.2017 | 0.8758 | 0.4846 | 0.046* | |
C14 | −0.2691 (2) | 0.66436 (19) | 0.45309 (10) | 0.0396 (3) | |
H14 | −0.3836 | 0.6639 | 0.4882 | 0.047* | |
C15 | −0.2080 (2) | 0.53636 (17) | 0.40304 (9) | 0.0355 (3) | |
C16 | −0.0384 (2) | 0.53634 (17) | 0.35082 (9) | 0.0336 (3) | |
H16 | 0.0020 | 0.4508 | 0.3176 | 0.040* | |
C17 | −0.2599 (2) | 0.2748 (2) | 0.36796 (13) | 0.0518 (4) | |
H17A | −0.3539 | 0.1994 | 0.3787 | 0.078* | |
H17B | −0.1370 | 0.2086 | 0.3939 | 0.078* | |
H17C | −0.2448 | 0.3208 | 0.3020 | 0.078* | |
C18 | 0.3358 (2) | 0.53685 (18) | 0.24300 (9) | 0.0353 (3) | |
H18A | 0.3293 | 0.4206 | 0.2818 | 0.042* | |
H18B | 0.4718 | 0.5408 | 0.2280 | 0.042* | |
C19 | 0.34447 (19) | 0.69401 (16) | 0.04920 (9) | 0.0311 (3) | |
C20 | 0.0686 (2) | 0.71676 (19) | −0.05329 (10) | 0.0407 (3) | |
H20A | −0.0043 | 0.6857 | 0.0042 | 0.049* | |
H20B | 0.0962 | 0.6156 | −0.0802 | 0.049* | |
C21 | −0.0524 (2) | 0.8689 (2) | −0.11983 (11) | 0.0441 (4) | |
H21A | −0.1690 | 0.8341 | −0.1351 | 0.053* | |
H21B | −0.0923 | 0.9658 | −0.0901 | 0.053* | |
C22 | 0.2181 (2) | 0.9831 (2) | −0.18091 (11) | 0.0497 (4) | |
H22A | 0.1762 | 1.0806 | −0.1518 | 0.060* | |
H22B | 0.2864 | 1.0260 | −0.2383 | 0.060* | |
C23 | 0.3561 (2) | 0.8398 (2) | −0.11672 (10) | 0.0430 (3) | |
H23A | 0.4142 | 0.7502 | −0.1491 | 0.052* | |
H23B | 0.4600 | 0.8887 | −0.0989 | 0.052* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0381 (2) | 0.0462 (2) | 0.0334 (2) | −0.01826 (16) | 0.00258 (14) | −0.01081 (15) |
S2 | 0.0298 (2) | 0.0622 (3) | 0.0451 (2) | −0.01602 (17) | −0.00144 (16) | −0.00997 (18) |
O3 | 0.0470 (6) | 0.0347 (5) | 0.0383 (5) | −0.0103 (4) | −0.0010 (4) | −0.0142 (4) |
O4 | 0.0665 (8) | 0.0560 (7) | 0.0859 (9) | −0.0322 (6) | 0.0105 (7) | −0.0352 (6) |
O5 | 0.0433 (6) | 0.0585 (7) | 0.0405 (6) | −0.0172 (5) | −0.0066 (5) | −0.0014 (5) |
O6 | 0.0432 (6) | 0.0412 (6) | 0.0627 (7) | −0.0158 (5) | 0.0115 (5) | −0.0164 (5) |
N7 | 0.0285 (6) | 0.0383 (6) | 0.0351 (6) | −0.0111 (5) | 0.0005 (5) | −0.0066 (5) |
C8 | 0.0440 (9) | 0.0426 (8) | 0.0438 (8) | −0.0140 (7) | −0.0039 (7) | −0.0118 (6) |
C9 | 0.0347 (8) | 0.0430 (8) | 0.0414 (8) | −0.0098 (6) | 0.0002 (6) | −0.0118 (6) |
C10 | 0.0328 (7) | 0.0316 (6) | 0.0278 (6) | −0.0024 (5) | −0.0047 (5) | −0.0045 (5) |
C11 | 0.0343 (7) | 0.0283 (6) | 0.0254 (6) | −0.0030 (5) | −0.0039 (5) | −0.0032 (5) |
C12 | 0.0397 (8) | 0.0283 (6) | 0.0274 (6) | −0.0052 (6) | −0.0052 (6) | −0.0044 (5) |
C13 | 0.0457 (9) | 0.0344 (7) | 0.0323 (7) | −0.0020 (6) | 0.0026 (6) | −0.0107 (6) |
C14 | 0.0400 (8) | 0.0397 (7) | 0.0356 (7) | −0.0049 (6) | 0.0065 (6) | −0.0067 (6) |
C15 | 0.0372 (8) | 0.0307 (7) | 0.0361 (7) | −0.0076 (6) | −0.0006 (6) | −0.0029 (5) |
C16 | 0.0397 (8) | 0.0279 (6) | 0.0331 (7) | −0.0042 (6) | 0.0001 (6) | −0.0090 (5) |
C17 | 0.0464 (9) | 0.0387 (8) | 0.0733 (11) | −0.0102 (7) | −0.0034 (8) | −0.0174 (8) |
C18 | 0.0342 (7) | 0.0351 (7) | 0.0344 (7) | −0.0033 (6) | −0.0012 (6) | −0.0072 (5) |
C19 | 0.0292 (7) | 0.0295 (6) | 0.0366 (7) | −0.0051 (5) | 0.0034 (5) | −0.0127 (5) |
C20 | 0.0337 (8) | 0.0456 (8) | 0.0436 (8) | −0.0170 (6) | −0.0039 (6) | −0.0041 (6) |
C21 | 0.0327 (8) | 0.0516 (9) | 0.0454 (8) | −0.0084 (7) | −0.0024 (6) | −0.0068 (7) |
C22 | 0.0481 (10) | 0.0533 (9) | 0.0456 (9) | −0.0225 (8) | −0.0038 (7) | 0.0023 (7) |
C23 | 0.0342 (8) | 0.0559 (9) | 0.0381 (8) | −0.0149 (7) | 0.0036 (6) | −0.0061 (7) |
S1—C19 | 1.7846 (13) | C13—C14 | 1.373 (2) |
S1—C18 | 1.8107 (14) | C13—H13 | 0.9300 |
S2—C19 | 1.6620 (14) | C14—C15 | 1.395 (2) |
O3—C8 | 1.3682 (18) | C14—H14 | 0.9300 |
O3—C12 | 1.3792 (16) | C15—C16 | 1.378 (2) |
O4—C8 | 1.2083 (18) | C16—H16 | 0.9300 |
O5—C21 | 1.4105 (19) | C17—H17A | 0.9600 |
O5—C22 | 1.4136 (19) | C17—H17B | 0.9600 |
O6—C15 | 1.3661 (17) | C17—H17C | 0.9600 |
O6—C17 | 1.4134 (19) | C18—H18A | 0.9700 |
N7—C19 | 1.3363 (17) | C18—H18B | 0.9700 |
N7—C20 | 1.4662 (18) | C20—C21 | 1.499 (2) |
N7—C23 | 1.4733 (18) | C20—H20A | 0.9700 |
C8—C9 | 1.440 (2) | C20—H20B | 0.9700 |
C9—C10 | 1.344 (2) | C21—H21A | 0.9700 |
C9—H9 | 0.9300 | C21—H21B | 0.9700 |
C10—C11 | 1.4453 (19) | C22—C23 | 1.504 (2) |
C10—C18 | 1.4995 (18) | C22—H22A | 0.9700 |
C11—C12 | 1.3909 (19) | C22—H22B | 0.9700 |
C11—C16 | 1.4028 (19) | C23—H23A | 0.9700 |
C12—C13 | 1.383 (2) | C23—H23B | 0.9700 |
C19—S1—C18 | 103.85 (6) | O6—C17—H17C | 109.5 |
C8—O3—C12 | 121.50 (11) | H17A—C17—H17C | 109.5 |
C21—O5—C22 | 109.50 (12) | H17B—C17—H17C | 109.5 |
C15—O6—C17 | 117.51 (12) | C10—C18—S1 | 111.36 (9) |
C19—N7—C20 | 124.03 (11) | C10—C18—H18A | 109.4 |
C19—N7—C23 | 120.79 (12) | S1—C18—H18A | 109.4 |
C20—N7—C23 | 113.08 (11) | C10—C18—H18B | 109.4 |
O4—C8—O3 | 117.00 (14) | S1—C18—H18B | 109.4 |
O4—C8—C9 | 126.27 (15) | H18A—C18—H18B | 108.0 |
O3—C8—C9 | 116.73 (12) | N7—C19—S2 | 124.57 (10) |
C10—C9—C8 | 122.97 (14) | N7—C19—S1 | 112.68 (10) |
C10—C9—H9 | 118.5 | S2—C19—S1 | 122.74 (8) |
C8—C9—H9 | 118.5 | N7—C20—C21 | 111.40 (12) |
C9—C10—C11 | 118.87 (13) | N7—C20—H20A | 109.3 |
C9—C10—C18 | 120.67 (13) | C21—C20—H20A | 109.3 |
C11—C10—C18 | 120.46 (12) | N7—C20—H20B | 109.3 |
C12—C11—C16 | 118.41 (13) | C21—C20—H20B | 109.3 |
C12—C11—C10 | 117.82 (12) | H20A—C20—H20B | 108.0 |
C16—C11—C10 | 123.77 (12) | O5—C21—C20 | 111.41 (12) |
O3—C12—C13 | 116.84 (12) | O5—C21—H21A | 109.3 |
O3—C12—C11 | 121.63 (12) | C20—C21—H21A | 109.3 |
C13—C12—C11 | 121.52 (13) | O5—C21—H21B | 109.3 |
C14—C13—C12 | 119.35 (13) | C20—C21—H21B | 109.3 |
C14—C13—H13 | 120.3 | H21A—C21—H21B | 108.0 |
C12—C13—H13 | 120.3 | O5—C22—C23 | 112.76 (13) |
C13—C14—C15 | 120.46 (13) | O5—C22—H22A | 109.0 |
C13—C14—H14 | 119.8 | C23—C22—H22A | 109.0 |
C15—C14—H14 | 119.8 | O5—C22—H22B | 109.0 |
O6—C15—C16 | 124.29 (13) | C23—C22—H22B | 109.0 |
O6—C15—C14 | 115.64 (13) | H22A—C22—H22B | 107.8 |
C16—C15—C14 | 120.07 (13) | N7—C23—C22 | 110.63 (12) |
C15—C16—C11 | 120.20 (12) | N7—C23—H23A | 109.5 |
C15—C16—H16 | 119.9 | C22—C23—H23A | 109.5 |
C11—C16—H16 | 119.9 | N7—C23—H23B | 109.5 |
O6—C17—H17A | 109.5 | C22—C23—H23B | 109.5 |
O6—C17—H17B | 109.5 | H23A—C23—H23B | 108.1 |
H17A—C17—H17B | 109.5 |
D—H···A | D—H | H···A | D···A | 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. |
Experimental details
Crystal data | |
Chemical formula | C16H17NO4S2 |
Mr | 351.43 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 785.49 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.24 × 0.20 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.770, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13583, 2725, 2482 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.073, 1.06 |
No. of reflections | 2725 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.15 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012).
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O6i | 0.93 | 2.5500 | 3.4582 (19) | 166.00 |
C17—H17B···O3ii | 0.96 | 2.5700 | 3.386 (2) | 143.00 |
C18—H18B···S2 | 0.97 | 2.5500 | 3.1527 (14) | 120.00 |
Symmetry codes: (i) −x−1, −y+1, −z+1; (ii) x, y−1, 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
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kumar, 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 Google Scholar
Sheldrick, G. M. (2007). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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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 π–π interactions between fused benzene Cg(3) (C11–C16) rings of chromene [shortest centroid–centroid distance = 3.5487 (8) Å] further stabilize the crystal packing