organic compounds
(7, 8-Dimethyl-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodithioate
aDepartment of Physics, SJB Institute of Technology, Kengeri, Bangalore 560 060, India, bDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore 570 006, India, and cSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India
*Correspondence e-mail: dorephy@gmail.com
In the title compound, C17H19NO3S2, the chromene unit makes a dihedral angle of 88.48 (5)° with the best plane through the morpholine ring. The carbodithioate group is present in an antiperiplanar conformation with respect to the morpholine ring, as indicated by the S—C—N—C torsion angle of −171.64 (8)°. The morpholine moiety adopts the usual chair conformation. The features C—H⋯O and C—H⋯S hydrogen bonds and C—H⋯π interactions.
Keywords: crystal structure; chromene derivatives; hydrogen bonds.
CCDC reference: 1447512
Structure description
et al., 2010) and anti-inflammatory (Eissa et al., 2009) properties. In addition, dithiocarbamic acid have gained a prominent role as cancer chemopreventive and anticancer agents (Scozzafava et al., 2000). In view of their importance, the determination of the title compound was carried out and the results are presented herein.
and its derivatives have drawn much attention in the field of current medicinal and pharmacological research and are reported to have a broad spectrum of biological activities, such as antimicrobial (RonadIn the molecular structure of the title compound (Fig. 1), the mean planes of the chromene unit and morpholine rings make a dihedral angle of 88.48 (5)°. The heterocyclic morpholine ring adopts a chair conformation with puckering parameters Q = 0.5323 (13) Å, θ = 10.75 (12)° and φ = 354.1 (8)°.
The two methyl groups are essentially coplanar with the chromene moiety, the maximum deviation from the mean plane being 0.040 (2) and 0.029 (2) Å for atoms C7 and C8, respectively. The carbodithioate group is present in an antiperiplanar conformation with respect to the morpholine ring, as indicated by the S2—C13—N1—C17 torsion angle of −171.64 (8)°. In the crystal, C12—H12B⋯O2 and C17—H17A⋯S2 hydrogen bonds (Table 1) result in the formation of chains along the b axis (Fig. 2). Parallel chains are linked by C—H⋯π interactions.
Synthesis and crystallization
4-Bromomethyl-6,7-dimethyl-chromen-2-one (3.9 g, 0.015 mol) and the potassium salt of morpholine-4-carboxylate (2.5 g, 0.015 mol) were dissolved in 35 ml of absolute ethanol and stirred at room temperature for 14 h. After completion of the reaction (monitored by TLC) ethanol was removed under reduced pressure. The solid obtained was extracted in ethyl acetate, washed with water, and the collected organic extract was dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the obtained solid product was crystallized from an ethanol:chloroform mixture (7:3) by slow evaporation.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1447512
10.1107/S2414314616000845/vm4005sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616000845/vm4005Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616000845/vm4005Isup3.cml
4-Bromomethyl-6,7-dimethyl-chromen-2-one 3.9 g (0.015 mol) and potassium salt of morpholine-4-carboxylate 2.5 g (0.015 mol) was dissolved in 35 ml of absolute ethanol and stirred at room temperature for 14 h. After completion of the reaction (monitored by TLC) ethanol was removed under reduced pressure. The solid obtained was extracted in ethyl acetate, washed with water, and the collected organic extract was dried over anhydrous Na2SO4. The solvent was removed under reduced pressure and the obtained solid product was crystallized from an ethanol:chloroform mixture (7:3) by slow evaporation.
Coumarins and its derivatives have drawn much attention in the field of current medicinal and pharmacological research and are reported to have a broad spectrum of biological activities, such as antimicrobial (Ronad et al., 2010) and anti-inflammatory (Eissa et al., 2009) properties. In addition, dithiocarbamic acid
have gained a prominent role as cancer chemopreventive and anticancer agents (Scozzafava et al., 2000). In view of their importance, the determination of the title compound was carried out and the results are presented herein.In the molecular structure of the title compound (Fig. 1), the mean planes of the chromene unit and morpholine rings make a dihedral angle of 88.48 (5)°. The heterocyclic morpholine ring adopts a chair conformation with puckering parameters Q = 0.5323 (13) Å, θ = 10.75 (12)° and φ = 354.1 (8)°.
The two methyl groups are essentially coplanar with the chromene moiety, the maximum deviation from the mean plane being 0.040 (2) and 0.029 (2) Å for atoms C7 and C8, respectively. The carbodithioate group is present in an antiperiplanar conformation with respect to the morpholine ring, as indicated by the S2—C13—N1—C17 torsion angle of −171.64 (8)°. In the crystal, C12—H12B···O2 and C17—H17A···S2 hydrogen bonds (Table 1) result in the formation of chains along the b axis (Fig. 2). Parallel chains interact by C—H···π bonds.
Data collection: APEX2 (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: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50° probability level. H atoms are represented as small circles. | |
Fig. 2. A crystal packing diagram of the title molecule, showing the C—H···O, C—H···S and C—H···π hydrogen bonds as red, yellow and gray dashed lines, respectively. |
C17H19NO3S2 | F(000) = 736 |
Mr = 349.47 | Dx = 1.375 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7073 reflections |
a = 16.0366 (5) Å | θ = 2.6–34.7° |
b = 7.8085 (2) Å | µ = 0.33 mm−1 |
c = 13.5083 (4) Å | T = 293 K |
β = 93.899 (1)° | Block, colourless |
V = 1687.62 (8) Å3 | 0.30 × 0.25 × 0.20 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | Rint = 0.027 |
ω and φ scans | θmax = 34.7°, θmin = 2.6° |
26234 measured reflections | h = −25→25 |
7073 independent reflections | k = −11→12 |
5320 reflections with I > 2σ(I) | l = −19→21 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.062P)2 + 0.1849P] where P = (Fo2 + 2Fc2)/3 |
7073 reflections | (Δ/σ)max = 0.001 |
210 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C17H19NO3S2 | V = 1687.62 (8) Å3 |
Mr = 349.47 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.0366 (5) Å | µ = 0.33 mm−1 |
b = 7.8085 (2) Å | T = 293 K |
c = 13.5083 (4) Å | 0.30 × 0.25 × 0.20 mm |
β = 93.899 (1)° |
Bruker APEXII CCD area-detector diffractometer | 5320 reflections with I > 2σ(I) |
26234 measured reflections | Rint = 0.027 |
7073 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.31 e Å−3 |
7073 reflections | Δρmin = −0.22 e Å−3 |
210 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | 0.13237 (2) | 0.68580 (3) | 0.11577 (2) | 0.0365 (1) | |
S2 | 0.06981 (2) | 0.86839 (4) | 0.29369 (2) | 0.0437 (1) | |
O1 | 0.34619 (5) | 1.17857 (10) | 0.08292 (7) | 0.0410 (3) | |
O2 | 0.29328 (8) | 1.33313 (12) | 0.19925 (9) | 0.0590 (4) | |
O3 | −0.17623 (6) | 0.83041 (14) | 0.01555 (8) | 0.0548 (3) | |
N1 | −0.02040 (5) | 0.79973 (11) | 0.12636 (6) | 0.0316 (2) | |
C1 | 0.31549 (6) | 0.87734 (13) | 0.06476 (9) | 0.0350 (3) | |
C2 | 0.32454 (8) | 0.72858 (16) | 0.00852 (11) | 0.0456 (3) | |
C3 | 0.36730 (9) | 0.7350 (2) | −0.07620 (11) | 0.0531 (4) | |
C4 | 0.40227 (8) | 0.8863 (2) | −0.10921 (10) | 0.0502 (4) | |
C5 | 0.39485 (7) | 1.03644 (17) | −0.05460 (10) | 0.0438 (3) | |
C6 | 0.35172 (6) | 1.02710 (14) | 0.03136 (9) | 0.0363 (3) | |
C7 | 0.44803 (10) | 0.8850 (3) | −0.20342 (13) | 0.0700 (6) | |
C8 | 0.43010 (10) | 1.2049 (2) | −0.08649 (13) | 0.0612 (5) | |
C9 | 0.30067 (7) | 1.19183 (14) | 0.16390 (10) | 0.0405 (3) | |
C10 | 0.26574 (7) | 1.03691 (14) | 0.20165 (9) | 0.0382 (3) | |
C11 | 0.27068 (6) | 0.88575 (13) | 0.15391 (8) | 0.0336 (3) | |
C12 | 0.22768 (7) | 0.73014 (14) | 0.19169 (9) | 0.0381 (3) | |
C13 | 0.05326 (6) | 0.79190 (11) | 0.17926 (7) | 0.0298 (2) | |
C14 | −0.09634 (7) | 0.85250 (16) | 0.17357 (9) | 0.0395 (3) | |
C15 | −0.15855 (8) | 0.93490 (18) | 0.10023 (10) | 0.0497 (4) | |
C16 | −0.10252 (8) | 0.80537 (17) | −0.03374 (9) | 0.0450 (3) | |
C17 | −0.03728 (7) | 0.71207 (14) | 0.03087 (8) | 0.0363 (3) | |
H2 | 0.30170 | 0.62580 | 0.02850 | 0.0550* | |
H3 | 0.37310 | 0.63520 | −0.11270 | 0.0640* | |
H7A | 0.44790 | 0.77100 | −0.23010 | 0.1050* | |
H7B | 0.50460 | 0.92200 | −0.18900 | 0.1050* | |
H7C | 0.42060 | 0.96110 | −0.25100 | 0.1050* | |
H8A | 0.42710 | 1.28700 | −0.03400 | 0.0920* | |
H8B | 0.39830 | 1.24550 | −0.14460 | 0.0920* | |
H8C | 0.48730 | 1.18960 | −0.10130 | 0.0920* | |
H10 | 0.23900 | 1.04120 | 0.26060 | 0.0460* | |
H12A | 0.21440 | 0.74900 | 0.25980 | 0.0460* | |
H12B | 0.26480 | 0.63220 | 0.19040 | 0.0460* | |
H14A | −0.08140 | 0.93270 | 0.22670 | 0.0470* | |
H14B | −0.12160 | 0.75310 | 0.20240 | 0.0470* | |
H15A | −0.20990 | 0.95680 | 0.13200 | 0.0600* | |
H15B | −0.13670 | 1.04400 | 0.07950 | 0.0600* | |
H16A | −0.08060 | 0.91560 | −0.05250 | 0.0540* | |
H16B | −0.11540 | 0.74000 | −0.09390 | 0.0540* | |
H17A | −0.05630 | 0.59640 | 0.04260 | 0.0440* | |
H17B | 0.01400 | 0.70480 | −0.00310 | 0.0440* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0347 (1) | 0.0342 (1) | 0.0411 (2) | −0.0005 (1) | 0.0070 (1) | −0.0070 (1) |
S2 | 0.0485 (2) | 0.0528 (2) | 0.0299 (1) | 0.0005 (1) | 0.0020 (1) | −0.0091 (1) |
O1 | 0.0395 (4) | 0.0336 (4) | 0.0495 (5) | −0.0047 (3) | 0.0010 (3) | 0.0009 (3) |
O2 | 0.0732 (7) | 0.0337 (4) | 0.0704 (7) | −0.0013 (4) | 0.0069 (5) | −0.0122 (4) |
O3 | 0.0412 (4) | 0.0720 (7) | 0.0500 (6) | 0.0100 (4) | −0.0062 (4) | −0.0159 (5) |
N1 | 0.0360 (4) | 0.0323 (4) | 0.0269 (4) | 0.0031 (3) | 0.0048 (3) | −0.0032 (3) |
C1 | 0.0303 (4) | 0.0334 (5) | 0.0412 (6) | 0.0018 (3) | 0.0014 (4) | −0.0015 (4) |
C2 | 0.0428 (6) | 0.0389 (5) | 0.0552 (7) | 0.0025 (4) | 0.0047 (5) | −0.0087 (5) |
C3 | 0.0484 (7) | 0.0572 (8) | 0.0538 (8) | 0.0086 (6) | 0.0047 (5) | −0.0162 (6) |
C4 | 0.0358 (5) | 0.0723 (9) | 0.0427 (7) | 0.0094 (5) | 0.0032 (5) | −0.0031 (6) |
C5 | 0.0313 (5) | 0.0565 (7) | 0.0432 (6) | 0.0008 (5) | 0.0007 (4) | 0.0073 (5) |
C6 | 0.0288 (4) | 0.0378 (5) | 0.0418 (6) | 0.0006 (4) | −0.0012 (4) | 0.0006 (4) |
C7 | 0.0518 (8) | 0.1087 (14) | 0.0507 (9) | 0.0115 (9) | 0.0131 (6) | −0.0033 (9) |
C8 | 0.0550 (8) | 0.0716 (9) | 0.0576 (9) | −0.0107 (7) | 0.0078 (6) | 0.0177 (7) |
C9 | 0.0394 (5) | 0.0335 (5) | 0.0476 (6) | 0.0002 (4) | −0.0034 (5) | −0.0042 (4) |
C10 | 0.0386 (5) | 0.0353 (5) | 0.0407 (6) | 0.0016 (4) | 0.0027 (4) | −0.0020 (4) |
C11 | 0.0293 (4) | 0.0310 (4) | 0.0401 (5) | 0.0021 (3) | −0.0005 (4) | 0.0021 (4) |
C12 | 0.0363 (5) | 0.0329 (5) | 0.0448 (6) | 0.0015 (4) | 0.0007 (4) | 0.0066 (4) |
C13 | 0.0372 (4) | 0.0245 (4) | 0.0281 (4) | −0.0008 (3) | 0.0060 (3) | 0.0004 (3) |
C14 | 0.0385 (5) | 0.0466 (6) | 0.0344 (5) | 0.0057 (4) | 0.0092 (4) | −0.0051 (4) |
C15 | 0.0458 (6) | 0.0536 (7) | 0.0493 (7) | 0.0148 (5) | 0.0005 (5) | −0.0106 (6) |
C16 | 0.0518 (6) | 0.0493 (6) | 0.0331 (6) | 0.0062 (5) | −0.0021 (5) | 0.0000 (4) |
C17 | 0.0436 (5) | 0.0372 (5) | 0.0281 (5) | 0.0049 (4) | 0.0030 (4) | −0.0057 (4) |
S1—C12 | 1.8152 (12) | C11—C12 | 1.5034 (15) |
S1—C13 | 1.7830 (10) | C14—C15 | 1.5021 (18) |
S2—C13 | 1.6616 (10) | C16—C17 | 1.5043 (17) |
O1—C6 | 1.3785 (14) | C2—H2 | 0.9300 |
O1—C9 | 1.3597 (16) | C3—H3 | 0.9300 |
O2—C9 | 1.2113 (15) | C7—H7A | 0.9600 |
O3—C15 | 1.4179 (17) | C7—H7B | 0.9600 |
O3—C16 | 1.4092 (16) | C7—H7C | 0.9600 |
N1—C13 | 1.3398 (13) | C8—H8A | 0.9600 |
N1—C14 | 1.4715 (14) | C8—H8B | 0.9600 |
N1—C17 | 1.4691 (14) | C8—H8C | 0.9600 |
C1—C2 | 1.4009 (17) | C10—H10 | 0.9300 |
C1—C6 | 1.3944 (15) | C12—H12A | 0.9700 |
C1—C11 | 1.4452 (15) | C12—H12B | 0.9700 |
C2—C3 | 1.375 (2) | C14—H14A | 0.9700 |
C3—C4 | 1.394 (2) | C14—H14B | 0.9700 |
C4—C5 | 1.395 (2) | C15—H15A | 0.9700 |
C4—C7 | 1.512 (2) | C15—H15B | 0.9700 |
C5—C6 | 1.3933 (17) | C16—H16A | 0.9700 |
C5—C8 | 1.506 (2) | C16—H16B | 0.9700 |
C9—C10 | 1.4408 (16) | C17—H17A | 0.9700 |
C10—C11 | 1.3499 (15) | C17—H17B | 0.9700 |
S1···C2 | 3.5093 (14) | C8···H7C | 2.9200 |
S2···C17i | 3.6412 (11) | C8···H7B | 2.9100 |
S2···C10 | 3.6988 (12) | C9···H8Bvii | 2.9700 |
S1···H2 | 3.0700 | C12···H2 | 2.7000 |
S1···H17B | 2.4100 | C13···H16Aiv | 2.9100 |
S1···H14Aii | 3.0600 | C13···H14Aii | 3.1000 |
S1···H17A | 3.2000 | C17···H17Aix | 3.0400 |
S2···H12A | 2.5700 | H2···S1 | 3.0700 |
S2···H14A | 2.5800 | H2···C12 | 2.7000 |
S2···H10 | 3.0900 | H2···H12B | 2.3000 |
S2···H14Bi | 3.1200 | H3···H7A | 2.3100 |
S2···H17Ai | 2.8600 | H7A···H3 | 2.3100 |
S2···H17Biii | 3.0000 | H7B···C8 | 2.9100 |
O1···O3iv | 2.9513 (13) | H7B···H8C | 2.4300 |
O2···C12v | 3.2731 (15) | H7B···O1vi | 2.8200 |
O3···O1iv | 2.9513 (13) | H7B···C6vi | 3.0600 |
O3···C10iv | 3.3421 (16) | H7C···C8 | 2.9200 |
O3···C6iv | 3.0524 (14) | H7C···O2x | 2.6500 |
O3···C9iv | 3.0382 (16) | H8A···O1 | 2.2700 |
O3···C1iv | 3.3230 (15) | H8B···C7 | 3.0500 |
O3···N1 | 2.8345 (13) | H8B···O2x | 2.6800 |
O1···H8A | 2.2700 | H8B···C9x | 2.9700 |
O1···H7Bvi | 2.8200 | H8C···C7 | 2.8000 |
O2···H8Bvii | 2.6800 | H8C···H7B | 2.4300 |
O2···H12Bv | 2.3800 | H10···S2 | 3.0900 |
O2···H15Ai | 2.8900 | H10···H12A | 2.3200 |
O2···H7Cvii | 2.6500 | H10···H14Bi | 2.5800 |
N1···O3 | 2.8345 (13) | H12A···S2 | 2.5700 |
C1···O3iv | 3.3230 (15) | H12A···H10 | 2.3200 |
C1···C15iv | 3.5620 (17) | H12B···O2viii | 2.3800 |
C2···S1 | 3.5093 (14) | H12B···C2 | 2.8000 |
C6···C15iv | 3.4778 (17) | H12B···H2 | 2.3000 |
C6···O3iv | 3.0524 (14) | H14A···S2 | 2.5800 |
C9···C16iv | 3.5256 (17) | H14A···S1i | 3.0600 |
C9···O3iv | 3.0382 (16) | H14A···C13i | 3.1000 |
C10···C16iv | 3.5644 (17) | H14B···S2ii | 3.1200 |
C10···S2 | 3.6988 (12) | H14B···H10ii | 2.5800 |
C10···O3iv | 3.3421 (16) | H15A···O2ii | 2.8900 |
C12···O2viii | 3.2731 (15) | H15A···C5iv | 3.0800 |
C15···C1iv | 3.5620 (17) | H15A···C6iv | 3.0600 |
C15···C6iv | 3.4778 (17) | H15B···H16A | 2.2800 |
C16···C10iv | 3.5644 (17) | H16A···H15B | 2.2800 |
C16···C9iv | 3.5256 (17) | H16A···C13iv | 2.9100 |
C17···S2ii | 3.6412 (11) | H17A···S1 | 3.2000 |
C2···H12B | 2.8000 | H17A···S2ii | 2.8600 |
C5···H15Aiv | 3.0800 | H17A···C17ix | 3.0400 |
C6···H7Bvi | 3.0600 | H17A···H17Bix | 2.5200 |
C6···H15Aiv | 3.0600 | H17B···S1 | 2.4100 |
C7···H8B | 3.0500 | H17B···H17Aix | 2.5200 |
C7···H8C | 2.8000 | H17B···S2xi | 3.0000 |
C12—S1—C13 | 103.82 (5) | C4—C7—H7A | 109.00 |
C6—O1—C9 | 121.89 (9) | C4—C7—H7B | 109.00 |
C15—O3—C16 | 109.44 (10) | C4—C7—H7C | 109.00 |
C13—N1—C14 | 120.48 (8) | H7A—C7—H7B | 109.00 |
C13—N1—C17 | 123.38 (8) | H7A—C7—H7C | 109.00 |
C14—N1—C17 | 113.73 (8) | H7B—C7—H7C | 109.00 |
C2—C1—C6 | 117.33 (11) | C5—C8—H8A | 109.00 |
C2—C1—C11 | 124.42 (10) | C5—C8—H8B | 109.00 |
C6—C1—C11 | 118.25 (10) | C5—C8—H8C | 109.00 |
C1—C2—C3 | 119.82 (12) | H8A—C8—H8B | 109.00 |
C2—C3—C4 | 122.11 (14) | H8A—C8—H8C | 110.00 |
C3—C4—C5 | 119.51 (12) | H8B—C8—H8C | 109.00 |
C3—C4—C7 | 119.51 (15) | C9—C10—H10 | 119.00 |
C5—C4—C7 | 120.98 (14) | C11—C10—H10 | 119.00 |
C4—C5—C6 | 117.51 (12) | S1—C12—H12A | 110.00 |
C4—C5—C8 | 122.39 (12) | S1—C12—H12B | 109.00 |
C6—C5—C8 | 120.09 (12) | C11—C12—H12A | 110.00 |
O1—C6—C1 | 120.90 (10) | C11—C12—H12B | 110.00 |
O1—C6—C5 | 115.39 (10) | H12A—C12—H12B | 108.00 |
C1—C6—C5 | 123.71 (11) | N1—C14—H14A | 109.00 |
O1—C9—O2 | 117.31 (11) | N1—C14—H14B | 109.00 |
O1—C9—C10 | 117.63 (10) | C15—C14—H14A | 109.00 |
O2—C9—C10 | 125.06 (12) | C15—C14—H14B | 109.00 |
C9—C10—C11 | 121.88 (11) | H14A—C14—H14B | 108.00 |
C1—C11—C10 | 119.11 (10) | O3—C15—H15A | 109.00 |
C1—C11—C12 | 120.78 (9) | O3—C15—H15B | 109.00 |
C10—C11—C12 | 120.09 (10) | C14—C15—H15A | 109.00 |
S1—C12—C11 | 110.51 (8) | C14—C15—H15B | 109.00 |
S1—C13—S2 | 122.73 (6) | H15A—C15—H15B | 108.00 |
S1—C13—N1 | 113.27 (7) | O3—C16—H16A | 109.00 |
S2—C13—N1 | 123.99 (7) | O3—C16—H16B | 109.00 |
N1—C14—C15 | 111.48 (10) | C17—C16—H16A | 109.00 |
O3—C15—C14 | 111.90 (11) | C17—C16—H16B | 109.00 |
O3—C16—C17 | 111.45 (10) | H16A—C16—H16B | 108.00 |
N1—C17—C16 | 111.29 (9) | N1—C17—H17A | 109.00 |
C1—C2—H2 | 120.00 | N1—C17—H17B | 109.00 |
C3—C2—H2 | 120.00 | C16—C17—H17A | 109.00 |
C2—C3—H3 | 119.00 | C16—C17—H17B | 109.00 |
C4—C3—H3 | 119.00 | H17A—C17—H17B | 108.00 |
C13—S1—C12—C11 | −93.89 (8) | C2—C1—C11—C10 | −179.63 (11) |
C12—S1—C13—S2 | −12.19 (7) | C2—C1—C11—C12 | −1.54 (17) |
C12—S1—C13—N1 | 169.21 (7) | C6—C1—C11—C10 | −0.26 (15) |
C9—O1—C6—C1 | −4.71 (16) | C6—C1—C11—C12 | 177.83 (10) |
C9—O1—C6—C5 | 174.95 (10) | C1—C2—C3—C4 | −0.3 (2) |
C6—O1—C9—O2 | −173.62 (11) | C2—C3—C4—C5 | 0.7 (2) |
C6—O1—C9—C10 | 7.02 (16) | C2—C3—C4—C7 | −179.57 (14) |
C16—O3—C15—C14 | −61.85 (14) | C3—C4—C5—C6 | −0.31 (18) |
C15—O3—C16—C17 | 62.58 (13) | C3—C4—C5—C8 | −179.20 (13) |
C14—N1—C13—S1 | 168.24 (8) | C7—C4—C5—C6 | 179.98 (11) |
C14—N1—C13—S2 | −10.34 (13) | C7—C4—C5—C8 | 1.1 (2) |
C17—N1—C13—S1 | 6.94 (12) | C4—C5—C6—O1 | 179.86 (10) |
C17—N1—C13—S2 | −171.64 (8) | C4—C5—C6—C1 | −0.50 (17) |
C13—N1—C14—C15 | 151.92 (10) | C8—C5—C6—O1 | −1.22 (16) |
C17—N1—C14—C15 | −45.09 (13) | C8—C5—C6—C1 | 178.42 (12) |
C13—N1—C17—C16 | −151.69 (10) | O1—C9—C10—C11 | −6.16 (17) |
C14—N1—C17—C16 | 45.88 (12) | O2—C9—C10—C11 | 174.54 (13) |
C6—C1—C2—C3 | −0.47 (18) | C9—C10—C11—C1 | 2.81 (16) |
C11—C1—C2—C3 | 178.91 (12) | C9—C10—C11—C12 | −175.29 (10) |
C2—C1—C6—O1 | −179.49 (10) | C1—C11—C12—S1 | −74.77 (11) |
C2—C1—C6—C5 | 0.89 (17) | C10—C11—C12—S1 | 103.30 (11) |
C11—C1—C6—O1 | 1.10 (15) | N1—C14—C15—O3 | 52.85 (14) |
C11—C1—C6—C5 | −178.53 (10) | O3—C16—C17—N1 | −54.64 (13) |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x, y−1/2, −z+1/2; (iii) x, −y+3/2, z+1/2; (iv) −x, −y+2, −z; (v) x, y+1, z; (vi) −x+1, −y+2, −z; (vii) x, −y+5/2, z+1/2; (viii) x, y−1, z; (ix) −x, −y+1, −z; (x) x, −y+5/2, z−1/2; (xi) x, −y+3/2, z−1/2. |
Cg is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···O2viii | 0.97 | 2.38 | 3.2731 (15) | 153 |
C17—H17A···S2ii | 0.97 | 2.86 | 3.6412 (11) | 138 |
C8—H8C···Cgvi | 0.96 | 2.93 | 3.6540 (17) | 133 |
Symmetry codes: (ii) −x, y−1/2, −z+1/2; (vi) −x+1, −y+2, −z; (viii) x, y−1, z. |
Cg is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···O2i | 0.9700 | 2.3800 | 3.2731 (15) | 153.00 |
C17—H17A···S2ii | 0.9700 | 2.8600 | 3.6412 (11) | 138.00 |
C8—H8C···Cgiii | 0.96 | 2.93 | 3.6540 (17) | 133 |
Symmetry codes: (i) x, y−1, z; (ii) −x, y−1/2, −z+1/2; (iii) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | C17H19NO3S2 |
Mr | 349.47 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 16.0366 (5), 7.8085 (2), 13.5083 (4) |
β (°) | 93.899 (1) |
V (Å3) | 1687.62 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26234, 7073, 5320 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.800 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.119, 1.02 |
No. of reflections | 7073 |
No. of parameters | 210 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.22 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
Acknowledgements
The authors would like to thank the SJB Institute of Technology, Kengeri, Bangalore, for their support. MM would also like to thank the UGC, New Delhi, Government of India, for awarding project F.41–920/2012(SR).
References
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Eissa, A. A. M., Farag, N. A. H. & Soliman, G. A. H. (2009). Bioorg. Med. Chem. 17, 5059–5070. CrossRef PubMed CAS Google Scholar
Ronad, P. M., Noolvi, M. N., Sapkal, S., Dharbhamulla, S. & Maddi, V. S. (2010). Eur. J. Med. Chem. 45, 85–89. CrossRef PubMed CAS Google Scholar
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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.
Coumarins and its derivatives have drawn more attention in the field of current medicinal and pharmacological research and reported to have a broad spectrum of biological activities, such as antimicrobial anti-microbial (Ronad et al., 2010) and anti-inflammatory (Eissa et al., 2009) agents. In addition, dithiocarbamic acid esters have gained prominent role due to their cancer chemopreventive and anti-cancer agent (Scozzafava et al., 2000). In view of their importance, the crystal structure determination of the title compound was carried out and the results are presented herein.
In the molecular structure of the title compound (Fig. 1), the mean planes through the chromene unit and the morpholine ring make a dihedral angle of 88.48 (5)°. The heterocyclic morpholine ring adopts a chair conformation with puckering parameters Q = 0.5323 (13) Å, θ = 10.75 (12)° and φ = 354.1 (8)° and the maximum deviation found on the puckered atom at N1 is 0.162 (1) Å.
Two methyl groups are essentially coplanar with the chromene moiety, the maximum deviation from the mean plane being −0.040 (2) Å and −0.029 (2) Å for atoms C7 and C8, respectively. The carbodithioate group is present in a -anti-periplanar (S2–C13–N1–C17) conformation with respect to the morpholine ring, as indicated by the torsion angle value of −171.64 (8)°. The crystal structure is stabilized by C8—H8A···O1 intramolecular and C17—H17A···S2 intermolecular hydrogen bonds. The molecular packing exhibits layered stacking when viewed down the b axis as shown in Fig. 2.