(5,7-Dimethyl-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodi­thio­ate

Anitha, B.R.; Roopashree, K.R.; Kumar, K.M.; Ravi, A.J.; Devarajegowda, H.C.

doi:10.1107/S2414314616001693

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160169

https://doi.org/10.1107/S2414314616001693

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(5,7-Dimethyl-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodithioate

B. R. Anitha,^a K. R. Roopashree,^a K. Mahesh Kumar,^b A. J. Ravi ^a and H. C. Devarajegowda ^a ^*

^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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 9 January 2016; accepted 27 January 2016; online 3 February 2016)

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 esters, a common class of organic molecules, have also attracted attention due to their anti-cancer action (Scozzafava 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 ).

The asymmetric unit is shown in Fig. 1. 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.

Table 1
Hydrogen-bond geometry (Å, °)

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.

Figure 1
Perspective diagram of the title molecule drawn with 50% probability displacement ellipsoids. H atoms are shown as spheres of arbitrary radius.

Figure 2
Packing diagram of the molecule viewed parallel to the b axis.

Synthesis 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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₉NO₃S₂
M_r	349.45
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	6.9573 (2), 7.9838 (2), 15.6037 (4)
α, β, γ (°)	75.485 (2), 87.122 (1), 75.763 (1)
V (Å³)	813.22 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.34
Crystal size (mm)	0.24 × 0.20 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.770, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12588, 2857, 2551
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.084, 1.08
No. of reflections	2857
No. of parameters	211
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.20
Computer programs: SMART (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC reference: 1450290

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616001693/hb4013sup1.cif

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

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2009); cell refinement: 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).

(5,7-Dimethyl-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodithioate top

Crystal data top

C₁₇H₁₉NO₃S₂	F(000) = 368
M_r = 349.45	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	2857 independent reflections
Radiation source: fine-focus sealed tube	2551 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω and φ scans	θ_max = 25.0°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
T_min = 0.770, T_max = 1.000	k = −9→9
12588 measured reflections	l = −18→18

Refinement top

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(F_o²) + (0.046P)² + 0.1658P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.084	(Δ/σ)_max = 0.001
S = 1.08	Δρ_max = 0.20 e Å⁻³
2857 reflections	Δρ_min = −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)

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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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