organic compounds
(5,7-Dimethyl-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, and bDepartment of Chemistry, Karnatak University's Karnatak Science College, Dharwad, Karnataka 580 001, India
*Correspondence e-mail: devarajegowda@yahoo.com
In the title compound, C17H19NO3S2, the 2H-chromene ring system is nearly planar, with a maximum deviation of 0.080 (2) Å, and the morpholine ring adopts a chair conformation. The bond-angle sum at the N atom is 358°. The coumarin unit makes dihedral angle of 86.34 (9)° with the morpholine ring. A short intramolecular C—H⋯S contact generates an S(7) ring. In the crystal, inversion dimers linked by pairs of weak C—H⋯O hydrogen bonds generate R22(16) loops. Aromatic π–π interactions interactions [shortest centroid–centroid distance = 3.8599 (13) Å] also occur.
Keywords: crystal structure; inversion dimers; hydrogen bonds; 2H-chromene; morpholine-4-carbodithioate ester.
CCDC reference: 1450290
Structure description
Recently, dithiocarbamic acid et al., 2000) in derivatives such as thalidomide dithiocarbamates (Zahran et al., 2008) and chromone dithiocarbamates (Huang et al., 2009). As part of our studies in this area, we now describe the structure of the title compound (Kant et al., 2012).
a common class of organic molecules, have also attracted attention due to their anti-cancer action (ScozzafavaThe . The 2H-chromene ring systems is nearly planar, with a maximum deviation of 0.0804 (22) Å for the atom C7 and the morpholine ring adopts a chair conformation. The coumarin unit makes dihedral angle of 86.34 (9)° with morpholine ring. In the crystal, C—H⋯O hydrogen bonds (Table 1, Fig. 2) and π–π interactions between fused benzene rings of chromene [shortest centroid–centroid distance = 3.8599 (13) Å] are observed.
is shown in Fig. 1Synthesis and crystallization
This compound was prepared according to the reported method (Kant 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. Yield = 81%, m.p. 445 K. IR (KBr): 645 cm−1(C—S), 1231 cm−1 (C=S), 1039 cm−1(C—O), 850 cm−1 (C—N),1118 cm−1(C—O—C), 1711 cm−1(C=O). GCMS: m/e: 349. 1H NMR (400 MHz, CDCl3, δ, p.p.m.) 2.21 (t, 3H, –CH3), 2.61 (t, 3H, –CH3), 3.61 (s, 4H, morpholine-CH2), 3.80 (s, 2H, morpholine-CH2), 4.15(s, 2H, morpholine-CH2), 4.65 (t, 2H, Methylene-CH2), 6.33 (s, 1H, Ar—H), 6.77 (s, 1H, Ar—H), 6.84 (s, 1H, Ar—H). Elemental analysis for C17H19NO3S2: C, 58.37; H, 5.42; N, 3.91.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1450290
https://doi.org/10.1107/S2414314616001693/hb4013sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616001693/hb4013Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314616001693/hb4013Isup3.cml
Data collection: SMART (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).C17H19NO3S2 | F(000) = 368 |
Mr = 349.45 | Dx = 1.427 Mg m−3 |
Triclinic, P1 | Melting point: 445 K |
a = 6.9573 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.9838 (2) Å | Cell parameters from 2857 reflections |
c = 15.6037 (4) Å | θ = 1.4–25.0° |
α = 75.485 (2)° | µ = 0.34 mm−1 |
β = 87.122 (1)° | T = 296 K |
γ = 75.763 (1)° | Plate, colourless |
V = 813.22 (4) Å3 | 0.24 × 0.20 × 0.12 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 2857 independent reflections |
Radiation source: fine-focus sealed tube | 2551 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω and φ scans | θmax = 25.0°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | h = −8→8 |
Tmin = 0.770, Tmax = 1.000 | k = −9→9 |
12588 measured reflections | l = −18→18 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.030 | w = 1/[σ2(Fo2) + (0.046P)2 + 0.1658P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.084 | (Δ/σ)max = 0.001 |
S = 1.08 | Δρmax = 0.20 e Å−3 |
2857 reflections | Δρmin = −0.20 e Å−3 |
211 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.041 (3) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.69951 (6) | 0.57313 (5) | 0.12898 (2) | 0.03649 (15) | |
S2 | 1.06731 (6) | 0.70892 (6) | 0.06881 (3) | 0.04197 (15) | |
O5 | 0.54406 (19) | 0.92765 (17) | −0.19357 (8) | 0.0492 (3) | |
O3 | 0.65176 (17) | 0.93171 (14) | 0.37562 (7) | 0.0371 (3) | |
O4 | 0.8819 (2) | 1.05956 (16) | 0.30663 (9) | 0.0512 (3) | |
N6 | 0.74909 (19) | 0.75809 (17) | −0.03019 (8) | 0.0328 (3) | |
C7 | 0.8041 (3) | 0.9362 (2) | 0.31725 (10) | 0.0367 (4) | |
C8 | 0.8592 (2) | 0.7900 (2) | 0.27620 (10) | 0.0352 (4) | |
H8 | 0.9736 | 0.7805 | 0.2425 | 0.042* | |
C9 | 0.7553 (2) | 0.66529 (19) | 0.28349 (9) | 0.0307 (3) | |
C10 | 0.5788 (2) | 0.67346 (19) | 0.33885 (9) | 0.0303 (3) | |
C11 | 0.5375 (2) | 0.80899 (19) | 0.38456 (9) | 0.0320 (3) | |
C12 | 0.3827 (3) | 0.8326 (2) | 0.44271 (10) | 0.0379 (4) | |
H12 | 0.3637 | 0.9241 | 0.4716 | 0.045* | |
C13 | 0.2570 (3) | 0.7202 (2) | 0.45765 (10) | 0.0385 (4) | |
C17 | 0.0869 (3) | 0.7390 (3) | 0.52080 (12) | 0.0503 (5) | |
H17A | 0.1041 | 0.8149 | 0.5573 | 0.076* | |
H17B | 0.0833 | 0.6237 | 0.5575 | 0.076* | |
H17C | −0.0353 | 0.7904 | 0.4879 | 0.076* | |
C14 | 0.2918 (3) | 0.5867 (2) | 0.41183 (11) | 0.0393 (4) | |
H14 | 0.2060 | 0.5112 | 0.4210 | 0.047* | |
C15 | 0.4458 (2) | 0.5596 (2) | 0.35363 (10) | 0.0354 (4) | |
C16 | 0.4565 (3) | 0.4090 (2) | 0.30953 (13) | 0.0523 (5) | |
H16A | 0.3469 | 0.3558 | 0.3282 | 0.078* | |
H16B | 0.5787 | 0.3208 | 0.3260 | 0.078* | |
H16C | 0.4507 | 0.4549 | 0.2464 | 0.078* | |
C18 | 0.8329 (2) | 0.5257 (2) | 0.23235 (10) | 0.0347 (4) | |
H18A | 0.8219 | 0.4104 | 0.2684 | 0.042* | |
H18B | 0.9723 | 0.5194 | 0.2201 | 0.042* | |
C19 | 0.8421 (2) | 0.69039 (19) | 0.04831 (10) | 0.0306 (3) | |
C20 | 0.5643 (2) | 0.7179 (2) | −0.05154 (11) | 0.0390 (4) | |
H20A | 0.4905 | 0.6889 | 0.0023 | 0.047* | |
H20B | 0.5961 | 0.6148 | −0.0765 | 0.047* | |
C21 | 0.4390 (3) | 0.8729 (2) | −0.11608 (11) | 0.0432 (4) | |
H21A | 0.3226 | 0.8400 | −0.1318 | 0.052* | |
H21B | 0.3945 | 0.9717 | −0.0884 | 0.052* | |
C22 | 0.7086 (3) | 0.9846 (2) | −0.17124 (12) | 0.0459 (4) | |
H22A | 0.6613 | 1.0835 | −0.1439 | 0.055* | |
H22B | 0.7775 | 1.0267 | −0.2249 | 0.055* | |
C23 | 0.8509 (3) | 0.8381 (2) | −0.10910 (11) | 0.0403 (4) | |
H23A | 0.9138 | 0.7468 | −0.1394 | 0.048* | |
H23B | 0.9537 | 0.8855 | −0.0911 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0415 (3) | 0.0421 (2) | 0.0314 (2) | −0.0195 (2) | 0.00148 (17) | −0.00998 (16) |
S2 | 0.0293 (2) | 0.0542 (3) | 0.0440 (3) | −0.0129 (2) | −0.00102 (18) | −0.01193 (19) |
O5 | 0.0426 (7) | 0.0605 (8) | 0.0402 (6) | −0.0188 (6) | −0.0063 (5) | 0.0033 (5) |
O3 | 0.0413 (7) | 0.0378 (6) | 0.0383 (6) | −0.0148 (5) | 0.0040 (5) | −0.0160 (5) |
O4 | 0.0559 (8) | 0.0475 (7) | 0.0639 (8) | −0.0285 (7) | 0.0133 (6) | −0.0251 (6) |
N6 | 0.0277 (7) | 0.0347 (7) | 0.0355 (7) | −0.0102 (6) | 0.0002 (5) | −0.0055 (5) |
C7 | 0.0368 (9) | 0.0392 (9) | 0.0369 (8) | −0.0124 (8) | −0.0012 (7) | −0.0110 (7) |
C8 | 0.0344 (9) | 0.0395 (9) | 0.0342 (8) | −0.0105 (7) | 0.0020 (7) | −0.0123 (6) |
C9 | 0.0335 (8) | 0.0290 (7) | 0.0267 (7) | −0.0031 (7) | −0.0051 (6) | −0.0050 (6) |
C10 | 0.0327 (8) | 0.0293 (7) | 0.0271 (7) | −0.0064 (7) | −0.0046 (6) | −0.0034 (6) |
C11 | 0.0341 (9) | 0.0305 (8) | 0.0315 (8) | −0.0089 (7) | −0.0040 (6) | −0.0060 (6) |
C12 | 0.0408 (10) | 0.0385 (9) | 0.0349 (8) | −0.0074 (8) | 0.0010 (7) | −0.0120 (7) |
C13 | 0.0348 (9) | 0.0421 (9) | 0.0340 (8) | −0.0062 (8) | −0.0001 (7) | −0.0037 (7) |
C17 | 0.0442 (11) | 0.0601 (11) | 0.0456 (10) | −0.0145 (9) | 0.0088 (8) | −0.0109 (8) |
C14 | 0.0377 (9) | 0.0397 (9) | 0.0410 (9) | −0.0157 (8) | −0.0009 (7) | −0.0041 (7) |
C15 | 0.0395 (9) | 0.0317 (8) | 0.0342 (8) | −0.0092 (7) | −0.0039 (7) | −0.0052 (6) |
C16 | 0.0590 (13) | 0.0466 (10) | 0.0644 (12) | −0.0286 (10) | 0.0127 (10) | −0.0243 (9) |
C18 | 0.0379 (9) | 0.0315 (8) | 0.0336 (8) | −0.0053 (7) | −0.0017 (7) | −0.0087 (6) |
C19 | 0.0305 (8) | 0.0266 (7) | 0.0356 (8) | −0.0046 (6) | 0.0019 (6) | −0.0116 (6) |
C20 | 0.0355 (9) | 0.0408 (9) | 0.0418 (9) | −0.0164 (8) | −0.0035 (7) | −0.0042 (7) |
C21 | 0.0319 (9) | 0.0474 (10) | 0.0468 (9) | −0.0107 (8) | −0.0033 (7) | −0.0035 (8) |
C22 | 0.0417 (10) | 0.0463 (10) | 0.0464 (10) | −0.0170 (8) | −0.0005 (8) | 0.0010 (8) |
C23 | 0.0327 (9) | 0.0468 (9) | 0.0384 (9) | −0.0114 (8) | 0.0042 (7) | −0.0039 (7) |
S1—C19 | 1.7850 (15) | C13—C17 | 1.505 (2) |
S1—C18 | 1.8104 (16) | C17—H17A | 0.9600 |
S2—C19 | 1.6634 (16) | C17—H17B | 0.9600 |
O5—C21 | 1.411 (2) | C17—H17C | 0.9600 |
O5—C22 | 1.419 (2) | C14—C15 | 1.381 (2) |
O3—C7 | 1.3636 (19) | C14—H14 | 0.9300 |
O3—C11 | 1.3837 (18) | C15—C16 | 1.513 (2) |
O4—C7 | 1.2088 (19) | C16—H16A | 0.9600 |
N6—C19 | 1.337 (2) | C16—H16B | 0.9600 |
N6—C23 | 1.472 (2) | C16—H16C | 0.9600 |
N6—C20 | 1.472 (2) | C18—H18A | 0.9700 |
C7—C8 | 1.432 (2) | C18—H18B | 0.9700 |
C8—C9 | 1.347 (2) | C20—C21 | 1.497 (2) |
C8—H8 | 0.9300 | C20—H20A | 0.9700 |
C9—C10 | 1.463 (2) | C20—H20B | 0.9700 |
C9—C18 | 1.509 (2) | C21—H21A | 0.9700 |
C10—C11 | 1.406 (2) | C21—H21B | 0.9700 |
C10—C15 | 1.422 (2) | C22—C23 | 1.499 (2) |
C11—C12 | 1.381 (2) | C22—H22A | 0.9700 |
C12—C13 | 1.373 (2) | C22—H22B | 0.9700 |
C12—H12 | 0.9300 | C23—H23A | 0.9700 |
C13—C14 | 1.394 (2) | C23—H23B | 0.9700 |
C19—S1—C18 | 104.75 (7) | C15—C16—H16A | 109.5 |
C21—O5—C22 | 109.33 (13) | C15—C16—H16B | 109.5 |
C7—O3—C11 | 121.95 (12) | H16A—C16—H16B | 109.5 |
C19—N6—C23 | 121.25 (13) | C15—C16—H16C | 109.5 |
C19—N6—C20 | 123.64 (13) | H16A—C16—H16C | 109.5 |
C23—N6—C20 | 113.10 (13) | H16B—C16—H16C | 109.5 |
O4—C7—O3 | 117.53 (14) | C9—C18—S1 | 112.31 (10) |
O4—C7—C8 | 126.46 (16) | C9—C18—H18A | 109.1 |
O3—C7—C8 | 115.98 (14) | S1—C18—H18A | 109.1 |
C9—C8—C7 | 123.98 (15) | C9—C18—H18B | 109.1 |
C9—C8—H8 | 118.0 | S1—C18—H18B | 109.1 |
C7—C8—H8 | 118.0 | H18A—C18—H18B | 107.9 |
C8—C9—C10 | 119.08 (14) | N6—C19—S2 | 124.20 (12) |
C8—C9—C18 | 116.07 (14) | N6—C19—S1 | 112.43 (11) |
C10—C9—C18 | 124.85 (13) | S2—C19—S1 | 123.36 (9) |
C11—C10—C15 | 115.86 (14) | N6—C20—C21 | 111.12 (13) |
C11—C10—C9 | 115.87 (13) | N6—C20—H20A | 109.4 |
C15—C10—C9 | 128.26 (14) | C21—C20—H20A | 109.4 |
C12—C11—O3 | 113.45 (13) | N6—C20—H20B | 109.4 |
C12—C11—C10 | 124.13 (14) | C21—C20—H20B | 109.4 |
O3—C11—C10 | 122.42 (14) | H20A—C20—H20B | 108.0 |
C13—C12—C11 | 119.55 (15) | O5—C21—C20 | 111.68 (14) |
C13—C12—H12 | 120.2 | O5—C21—H21A | 109.3 |
C11—C12—H12 | 120.2 | C20—C21—H21A | 109.3 |
C12—C13—C14 | 117.62 (15) | O5—C21—H21B | 109.3 |
C12—C13—C17 | 121.79 (16) | C20—C21—H21B | 109.3 |
C14—C13—C17 | 120.59 (16) | H21A—C21—H21B | 107.9 |
C13—C17—H17A | 109.5 | O5—C22—C23 | 112.16 (14) |
C13—C17—H17B | 109.5 | O5—C22—H22A | 109.2 |
H17A—C17—H17B | 109.5 | C23—C22—H22A | 109.2 |
C13—C17—H17C | 109.5 | O5—C22—H22B | 109.2 |
H17A—C17—H17C | 109.5 | C23—C22—H22B | 109.2 |
H17B—C17—H17C | 109.5 | H22A—C22—H22B | 107.9 |
C15—C14—C13 | 124.03 (15) | N6—C23—C22 | 111.21 (14) |
C15—C14—H14 | 118.0 | N6—C23—H23A | 109.4 |
C13—C14—H14 | 118.0 | C22—C23—H23A | 109.4 |
C14—C15—C10 | 118.78 (15) | N6—C23—H23B | 109.4 |
C14—C15—C16 | 115.96 (15) | C22—C23—H23B | 109.4 |
C10—C15—C16 | 125.25 (15) | H23A—C23—H23B | 108.0 |
C11—O3—C7—O4 | 172.02 (14) | C13—C14—C15—C16 | −179.20 (16) |
C11—O3—C7—C8 | −9.6 (2) | C11—C10—C15—C14 | −1.4 (2) |
O4—C7—C8—C9 | −173.11 (16) | C9—C10—C15—C14 | 177.29 (14) |
O3—C7—C8—C9 | 8.7 (2) | C11—C10—C15—C16 | 177.88 (15) |
C7—C8—C9—C10 | −2.2 (2) | C9—C10—C15—C16 | −3.5 (3) |
C7—C8—C9—C18 | 177.64 (14) | C8—C9—C18—S1 | −99.37 (15) |
C8—C9—C10—C11 | −3.3 (2) | C10—C9—C18—S1 | 80.51 (16) |
C18—C9—C10—C11 | 176.86 (13) | C19—S1—C18—C9 | 94.28 (12) |
C8—C9—C10—C15 | 178.07 (14) | C23—N6—C19—S2 | 7.4 (2) |
C18—C9—C10—C15 | −1.8 (2) | C20—N6—C19—S2 | 170.20 (12) |
C7—O3—C11—C12 | −176.06 (13) | C23—N6—C19—S1 | −171.43 (11) |
C7—O3—C11—C10 | 4.5 (2) | C20—N6—C19—S1 | −8.65 (19) |
C15—C10—C11—C12 | 1.7 (2) | C18—S1—C19—N6 | −171.04 (11) |
C9—C10—C11—C12 | −177.11 (14) | C18—S1—C19—S2 | 10.10 (12) |
C15—C10—C11—O3 | −178.87 (13) | C19—N6—C20—C21 | 148.50 (15) |
C9—C10—C11—O3 | 2.3 (2) | C23—N6—C20—C21 | −47.48 (19) |
O3—C11—C12—C13 | 179.83 (14) | C22—O5—C21—C20 | −61.97 (19) |
C10—C11—C12—C13 | −0.7 (2) | N6—C20—C21—O5 | 55.36 (19) |
C11—C12—C13—C14 | −0.6 (2) | C21—O5—C22—C23 | 61.16 (19) |
C11—C12—C13—C17 | 179.55 (15) | C19—N6—C23—C22 | −148.99 (15) |
C12—C13—C14—C15 | 0.9 (3) | C20—N6—C23—C22 | 46.56 (19) |
C17—C13—C14—C15 | −179.25 (15) | O5—C22—C23—N6 | −53.5 (2) |
C13—C14—C15—C10 | 0.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C16—H16C···S1 | 0.96 | 2.62 | 3.358 (2) | 134 |
C17—H17A···O4i | 0.96 | 2.58 | 3.505 (2) | 162 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Acknowledgements
The authors thank the Universities Sophisticated Instrumental Centre, Karnatak University, Dharwad, for the X-ray data collection.
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