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

Devarajegowda, H.C.; Kumar, K.M.; Seenivasa, S.; Arunkashi, H.K.; Kotresh, O.

doi:10.1107/S1600536812051847

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

H. C. Devarajegowda, K. M. Kumar, S. Seenivasa, H. K. Arunkashi and O. Kotresh

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].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536812051847/gw2129sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536812051847/gw2129Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536812051847/gw2129Isup3.cml Supplementary material

CCDC reference: 925150

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.002 Å
R factor = 0.027
wR factor = 0.073
Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S2     --  C19     ..        6.3 su
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         50
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          3

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00400 Deg.
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          78 Perc.
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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 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

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.

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

	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.
	Fig. 2. The packing of molecules.

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

Crystal data top

C₁₆H₁₇NO₄S₂	Z = 2
M_r = 351.43	F(000) = 368
Triclinic, P1	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	2725 independent reflections
Radiation source: fine-focus sealed tube	2482 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	h = −8→8
T_min = 0.770, T_max = 1.000	k = −9→9
13583 measured reflections	l = −17→17

Refinement top

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(F_o²) + (0.0403P)² + 0.1479P] where P = (F_o² + 2F_c²)/3
2725 reflections	(Δ/σ)_max = 0.001
208 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₆H₁₇NO₄S₂	γ = 78.355 (4)°
M_r = 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)°

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)
T_min = 0.770, T_max = 1.000	R_int = 0.024
13583 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
2725 reflections	Δρ_min = −0.15 e Å⁻³
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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.770, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13583, 2725, 2482
R_int	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
Δρ_max, Δρ_min (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).