Crystal structure of (6-bromo-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodi­thio­ate

Kumar, K.M.; Roopashree, K.R.; Vinduvahini, M.; Kotresh, O.; Devarajegowda, H.C.

doi:10.1107/S2056989015011007

Crystal structure of (6-bromo-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodithioate

K. M. Kumar, K. R. Roopashree, M. Vinduvahini, O. Kotresh and H. C. Devarajegowda

In the title compound, C₁₅H₁₄BrNO₃S₂, the 2H-chromene ring system is nearly planar, with a maximum deviation of 0.034 (2) Å, and the morpholine ring adopts a chair conformation. The dihedral angle between best plane through the 2H-chromene ring system and the morpholine ring is 86.32 (9)°. Intramolecular C—H

S hydrogen bonds are observed. In the crystal, inversion-related C—H

S and C—H

O interactions generate R₂²(10) and R₂²(8) rings patterns, respectively. In addition, the crystal packing features π–π interactions between fused benzene rings [centroid–centroid distance = 3.7558 (12) Å].

Keywords: crystal structure; coumarins; dithiocarbamates; biological applications; hydrogen bonding; π–π interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015011007/bq2399sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989015011007/bq2399Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015011007/bq2399Isup3.cml Supplementary material

CCDC reference: 1405247

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.003 Å
R factor = 0.026
wR factor = 0.065
Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         14 Report

Alert level G
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ..........    0.00200 Degree
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report

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

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

Comment top

In recent years, much attention has been directed towards the synthesis of substituted coumarins owing to their tremendous application in various research fields including biological science and medicinal chemistry. Substituted coumarin derivatives are components of numerous natural products like warfarin, phenprocoumon, coumatetralyl, carbochromen, bromadialone, etc. These compounds also exhibit a wide band of biological activities including antibacterial, anti-HIV (Hesse & Kirsch, 2002), antiviral (Lee et al., 1998), anticoagulant (Jung et al., 2001), antioxidant (Melagraki et al., 2009) and anticancer activities (Jung et al.,(2004). Carbon–sulfur bond formation is a fundamental approach to bring sulfur into organic compounds, and this has received much attention due to its occurrence in many molecules that are of biological and pharmaceutical importance. The antibacterial and antifungal activities of dithiocarbamates were reported to arise by the reaction with HS-groups of the physiologically important enzymes by transferring the alkyl group of the dithioester to the HS-function of the enzyme (Schönenberger & Lippert, 1972). Organic dithiocarbamates, ubiquitously found in a variety of biologically active molecules (Dhooghe & De Kimpe, 2006), are of high importance in academia as well as in industry.

In view of the various physiological activities of coumarins and dithiocarbamates, our current studies are focused on the development of new routes for the synthesis of coumarins incorporating dithiocarbamate moieties.

The asymmetric unit of (6-bromo-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodi thioate is shown in Fig. 1. The 2H-chromene ring systems is nearly planar, with a maximum deviation of 0.0337 (23) Å for the atom C16 and the morpholine ring adopts a chair conformation. The dihedral angle between the 2H-chromene ring and the morpholine ring is 86.32 (9) °. In the crystal structure, intermolecular C—H···O and intramolecular C–H···S hydrogen bonds are observed (Table 1) and inversion related C—H···S and C—H···O interactions generate R₂ ²(10) and R₂ ²(8) rings pattern respectively. In addition, the crystal packing is stabilized by π–π [C_g (3)– C_g(3);C8–C13] interactions between fused benzene rings [centroid- centroid distance = 3.7558 (12)].

Related literature top

For biological applications of coumarins and dithiocarbamates, see: Dhooghe & De Kimpe (2006); Hesse & Kirsch (2002); Jung et al. (2001, 2004); Lee et al. (1998); Melagraki et al. (2009); Schönenberger & Lippert (1972). For standard bond lengths, see: Devarajegowda et al. (2013). For a related structure and the synthesis of the title compound, see: Devarajegowda et al. (2013).

Experimental top

All the chemicals used were of analytical reagent grade and were used directly without further purification. The title compound was synthesized according to the reported method (Devarajegowda et al., 2013). The compound is recrystallized by ethanol-chloroform mixture. Colourless needles of the title compound were grown from a mixed solution of Ethanol/Chloroform (V/V = 2/1) by slow evaporation at room temperature. Yield =72%, m.p.: 433–435 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: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

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. Crystal packing for the title compound with hydrogen bonds drawn as dashed lines.

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

Crystal data top

C₁₅H₁₄BrNO₃S₂	F(000) = 404
M_r = 400.30	D_x = 1.704 Mg m⁻³
Triclinic, P1	Melting point: 435 K
a = 7.0500 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.6049 (3) Å	Cell parameters from 3224 reflections
c = 15.1376 (7) Å	θ = 2.7–26.5°
α = 78.782 (2)°	µ = 2.91 mm⁻¹
β = 88.549 (2)°	T = 296 K
γ = 78.515 (2)°	Plate, colourless
V = 780.07 (6) Å³	0.24 × 0.20 × 0.12 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	3224 independent reflections
Radiation source: fine-focus sealed tube	2806 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ω and ϕ scans	θ_max = 26.5°, θ_min = 2.7°
Absorption correction: ψ scan (SADABS; Sheldrick, 2007)	h = −8→8
T_min = 0.770, T_max = 1.000	k = −9→9
13789 measured reflections	l = −18→18

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0328P)² + 0.2957P] where P = (F_o² + 2F_c²)/3
3224 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₁₅H₁₄BrNO₃S₂	γ = 78.515 (2)°
M_r = 400.30	V = 780.07 (6) Å³
Triclinic, P1	Z = 2
a = 7.0500 (3) Å	Mo Kα radiation
b = 7.6049 (3) Å	µ = 2.91 mm⁻¹
c = 15.1376 (7) Å	T = 296 K
α = 78.782 (2)°	0.24 × 0.20 × 0.12 mm
β = 88.549 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3224 independent reflections
Absorption correction: ψ scan (SADABS; Sheldrick, 2007)	2806 reflections with I > 2σ(I)
T_min = 0.770, T_max = 1.000	R_int = 0.027
13789 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.03	Δρ_max = 0.26 e Å⁻³
3224 reflections	Δρ_min = −0.43 e Å⁻³
199 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Br1	0.19477 (3)	0.33461 (3)	0.89681 (2)	0.05002 (9)
S2	0.70559 (7)	0.58659 (7)	0.62666 (3)	0.03418 (12)
S3	1.06683 (7)	0.72703 (8)	0.56091 (3)	0.03905 (13)
O6	0.5420 (2)	0.9077 (2)	0.29823 (10)	0.0520 (4)
O4	0.6263 (2)	0.94245 (19)	0.89038 (9)	0.0404 (3)
O5	0.8534 (3)	1.0955 (2)	0.84135 (14)	0.0650 (5)
N7	0.7479 (2)	0.7625 (2)	0.46382 (10)	0.0303 (3)
C8	0.3315 (3)	0.5266 (3)	0.89259 (13)	0.0373 (4)
C9	0.4939 (3)	0.5289 (3)	0.84039 (12)	0.0337 (4)
H9	0.5346	0.4379	0.8070	0.040*
C10	0.5976 (3)	0.6687 (2)	0.83777 (11)	0.0299 (4)
C11	0.5313 (3)	0.8021 (3)	0.88881 (12)	0.0345 (4)
C12	0.3686 (3)	0.7987 (3)	0.94128 (14)	0.0441 (5)
H12	0.3272	0.8889	0.9750	0.053*
C13	0.2683 (3)	0.6601 (3)	0.94310 (14)	0.0450 (5)
H13	0.1585	0.6561	0.9782	0.054*
C14	0.7717 (3)	0.6820 (2)	0.78610 (11)	0.0302 (4)
C15	0.8595 (3)	0.8222 (3)	0.78884 (14)	0.0381 (4)
H15	0.9729	0.8289	0.7567	0.046*
C16	0.7858 (3)	0.9630 (3)	0.83943 (15)	0.0428 (5)
C17	0.8495 (3)	0.5444 (3)	0.72867 (12)	0.0328 (4)
H17A	0.8481	0.4223	0.7622	0.039*
H17B	0.9826	0.5515	0.7133	0.039*
C18	0.8436 (2)	0.7021 (2)	0.54254 (12)	0.0275 (4)
C19	0.5618 (3)	0.7172 (3)	0.44561 (14)	0.0392 (5)
H19A	0.4913	0.6973	0.5014	0.047*
H19B	0.5848	0.6047	0.4223	0.047*
C20	0.4422 (3)	0.8674 (3)	0.37879 (14)	0.0418 (5)
H20A	0.3232	0.8309	0.3659	0.050*
H20B	0.4081	0.9764	0.4047	0.050*
C21	0.7118 (3)	0.9691 (4)	0.31608 (16)	0.0503 (6)
H21A	0.6753	1.0799	0.3403	0.060*
H21B	0.7785	0.9988	0.2600	0.060*
C22	0.8474 (3)	0.8295 (3)	0.38134 (13)	0.0381 (4)
H22A	0.9027	0.7273	0.3530	0.046*
H22B	0.9525	0.8835	0.3969	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.04201 (14)	0.05131 (15)	0.05488 (15)	−0.01752 (10)	−0.00222 (10)	0.00309 (10)
S2	0.0345 (2)	0.0421 (3)	0.0294 (2)	−0.0157 (2)	0.00236 (18)	−0.00731 (19)
S3	0.0262 (2)	0.0502 (3)	0.0414 (3)	−0.0118 (2)	−0.00145 (19)	−0.0059 (2)
O6	0.0422 (8)	0.0743 (11)	0.0365 (8)	−0.0190 (8)	−0.0082 (6)	0.0050 (7)
O4	0.0543 (9)	0.0348 (7)	0.0348 (7)	−0.0096 (6)	−0.0005 (6)	−0.0120 (6)
O5	0.0792 (13)	0.0475 (10)	0.0813 (13)	−0.0312 (9)	0.0080 (10)	−0.0262 (9)
N7	0.0259 (7)	0.0327 (8)	0.0322 (8)	−0.0083 (6)	0.0005 (6)	−0.0036 (6)
C8	0.0350 (10)	0.0413 (11)	0.0321 (10)	−0.0085 (9)	−0.0031 (8)	0.0025 (8)
C9	0.0386 (10)	0.0339 (10)	0.0278 (9)	−0.0064 (8)	−0.0018 (8)	−0.0047 (7)
C10	0.0356 (9)	0.0293 (9)	0.0225 (8)	−0.0036 (7)	−0.0026 (7)	−0.0022 (7)
C11	0.0438 (11)	0.0321 (10)	0.0260 (9)	−0.0038 (8)	−0.0029 (8)	−0.0052 (7)
C12	0.0507 (12)	0.0463 (12)	0.0335 (10)	−0.0010 (10)	0.0067 (9)	−0.0133 (9)
C13	0.0392 (11)	0.0562 (14)	0.0358 (11)	−0.0049 (10)	0.0067 (9)	−0.0052 (10)
C14	0.0330 (9)	0.0296 (9)	0.0256 (8)	−0.0035 (7)	−0.0032 (7)	−0.0018 (7)
C15	0.0382 (10)	0.0375 (11)	0.0395 (10)	−0.0099 (8)	0.0014 (8)	−0.0073 (8)
C16	0.0522 (13)	0.0352 (11)	0.0422 (11)	−0.0112 (9)	−0.0040 (10)	−0.0072 (9)
C17	0.0335 (10)	0.0327 (10)	0.0304 (9)	−0.0033 (8)	0.0009 (7)	−0.0054 (8)
C18	0.0269 (9)	0.0238 (8)	0.0325 (9)	−0.0037 (7)	0.0026 (7)	−0.0089 (7)
C19	0.0309 (10)	0.0447 (12)	0.0419 (11)	−0.0153 (9)	−0.0047 (8)	0.0005 (9)
C20	0.0305 (10)	0.0471 (12)	0.0449 (11)	−0.0067 (9)	−0.0030 (8)	−0.0022 (9)
C21	0.0423 (12)	0.0611 (15)	0.0435 (12)	−0.0203 (11)	−0.0036 (9)	0.0103 (11)
C22	0.0293 (9)	0.0480 (12)	0.0356 (10)	−0.0085 (9)	0.0050 (8)	−0.0044 (9)

Geometric parameters (Å, º) top

Br1—C8	1.894 (2)	C12—C13	1.377 (3)
S2—C18	1.7839 (18)	C12—H12	0.9300
S2—C17	1.8095 (19)	C13—H13	0.9300
S3—C18	1.6585 (18)	C14—C15	1.343 (3)
O6—C20	1.405 (3)	C14—C17	1.501 (3)
O6—C21	1.418 (3)	C15—C16	1.442 (3)
O4—C16	1.365 (3)	C15—H15	0.9300
O4—C11	1.373 (2)	C17—H17A	0.9700
O5—C16	1.202 (3)	C17—H17B	0.9700
N7—C18	1.338 (2)	C19—C20	1.500 (3)
N7—C19	1.466 (2)	C19—H19A	0.9700
N7—C22	1.470 (2)	C19—H19B	0.9700
C8—C9	1.376 (3)	C20—H20A	0.9700
C8—C13	1.385 (3)	C20—H20B	0.9700
C9—C10	1.400 (3)	C21—C22	1.501 (3)
C9—H9	0.9300	C21—H21A	0.9700
C10—C11	1.394 (3)	C21—H21B	0.9700
C10—C14	1.448 (3)	C22—H22A	0.9700
C11—C12	1.380 (3)	C22—H22B	0.9700

C18—S2—C17	104.28 (9)	C14—C17—S2	110.63 (13)
C20—O6—C21	109.57 (16)	C14—C17—H17A	109.5
C16—O4—C11	121.90 (15)	S2—C17—H17A	109.5
C18—N7—C19	123.45 (15)	C14—C17—H17B	109.5
C18—N7—C22	121.02 (15)	S2—C17—H17B	109.5
C19—N7—C22	112.94 (15)	H17A—C17—H17B	108.1
C9—C8—C13	121.3 (2)	N7—C18—S3	124.57 (14)
C9—C8—Br1	119.16 (16)	N7—C18—S2	112.39 (13)
C13—C8—Br1	119.54 (16)	S3—C18—S2	123.03 (11)
C8—C9—C10	119.64 (18)	N7—C19—C20	111.25 (16)
C8—C9—H9	120.2	N7—C19—H19A	109.4
C10—C9—H9	120.2	C20—C19—H19A	109.4
C11—C10—C9	118.19 (18)	N7—C19—H19B	109.4
C11—C10—C14	117.86 (17)	C20—C19—H19B	109.4
C9—C10—C14	123.94 (17)	H19A—C19—H19B	108.0
O4—C11—C12	116.55 (18)	O6—C20—C19	111.60 (17)
O4—C11—C10	121.57 (18)	O6—C20—H20A	109.3
C12—C11—C10	121.87 (19)	C19—C20—H20A	109.3
C13—C12—C11	119.2 (2)	O6—C20—H20B	109.3
C13—C12—H12	120.4	C19—C20—H20B	109.3
C11—C12—H12	120.4	H20A—C20—H20B	108.0
C12—C13—C8	119.8 (2)	O6—C21—C22	112.72 (18)
C12—C13—H13	120.1	O6—C21—H21A	109.0
C8—C13—H13	120.1	C22—C21—H21A	109.0
C15—C14—C10	118.75 (17)	O6—C21—H21B	109.0
C15—C14—C17	120.61 (18)	C22—C21—H21B	109.0
C10—C14—C17	120.62 (16)	H21A—C21—H21B	107.8
C14—C15—C16	122.92 (19)	N7—C22—C21	111.57 (16)
C14—C15—H15	118.5	N7—C22—H22A	109.3
C16—C15—H15	118.5	C21—C22—H22A	109.3
O5—C16—O4	117.3 (2)	N7—C22—H22B	109.3
O5—C16—C15	125.9 (2)	C21—C22—H22B	109.3
O4—C16—C15	116.84 (18)	H22A—C22—H22B	108.0

C13—C8—C9—C10	−0.2 (3)	C11—O4—C16—O5	176.05 (19)
Br1—C8—C9—C10	−179.11 (13)	C11—O4—C16—C15	−4.6 (3)
C8—C9—C10—C11	0.0 (3)	C14—C15—C16—O5	−176.7 (2)
C8—C9—C10—C14	179.09 (17)	C14—C15—C16—O4	4.1 (3)
C16—O4—C11—C12	−178.20 (18)	C15—C14—C17—S2	−102.79 (18)
C16—O4—C11—C10	2.7 (3)	C10—C14—C17—S2	75.62 (18)
C9—C10—C11—O4	179.34 (16)	C18—S2—C17—C14	100.78 (14)
C14—C10—C11—O4	0.2 (3)	C19—N7—C18—S3	171.30 (15)
C9—C10—C11—C12	0.3 (3)	C22—N7—C18—S3	10.9 (3)
C14—C10—C11—C12	−178.90 (18)	C19—N7—C18—S2	−7.7 (2)
O4—C11—C12—C13	−179.37 (18)	C22—N7—C18—S2	−168.15 (14)
C10—C11—C12—C13	−0.3 (3)	C17—S2—C18—N7	−173.01 (13)
C11—C12—C13—C8	0.0 (3)	C17—S2—C18—S3	7.95 (14)
C9—C8—C13—C12	0.2 (3)	C18—N7—C19—C20	150.27 (18)
Br1—C8—C13—C12	179.12 (16)	C22—N7—C19—C20	−47.9 (2)
C11—C10—C14—C15	−0.7 (3)	C21—O6—C20—C19	−61.6 (2)
C9—C10—C14—C15	−179.84 (17)	N7—C19—C20—O6	56.1 (2)
C11—C10—C14—C17	−179.15 (16)	C20—O6—C21—C22	59.8 (3)
C9—C10—C14—C17	1.7 (3)	C18—N7—C22—C21	−151.82 (19)
C10—C14—C15—C16	−1.5 (3)	C19—N7—C22—C21	45.8 (2)
C17—C14—C15—C16	176.98 (18)	O6—C21—C22—N7	−51.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17A···O5ⁱ	0.97	2.53	3.501 (2)	176
C17—H17B···S3	0.97	2.55	3.1633 (16)	121
C19—H19A···S2	0.97	2.37	2.864 (2)	111
C22—H22B···S3	0.97	2.61	3.0486 (19)	108

Symmetry code: (i) x, y−1, z.