Crystal structure of (6-bromo-2-oxo-2H-chromen-4-yl)methyl morpholine-4-carbodi-thio-ate.

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)°. Intra-molecular C-H⋯S hydrogen bonds are observed. In the crystal, inversion-related C-H⋯S and C-H⋯O inter-actions generate R 2 (2)(10) and R 2 (2)(8) rings patterns, respectively. In addition, the crystal packing features π-π inter-actions between fused benzene rings [centroid-centroid distance = 3.7558 (12) Å].

Related literature

For biological applications of coumarins and di­thio­carbamates, see: D’hooghe & 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

Crystal data

C15H14BrNO3S2

M = 400.30

Triclinic,

a = 7.0500 (3) Å

b = 7.6049 (3) Å

c = 15.1376 (7) Å

α = 78.782 (2)°

β = 88.549 (2)°

γ = 78.515 (2)°

V = 780.07 (6) Å3

Z = 2

Mo Kα radiation

μ = 2.91 mm−1

T = 296 K

0.24 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: ψ scan (SADABS; Sheldrick, 2007 ▸) T min = 0.770, T max = 1.000

13789 measured reflections

3224 independent reflections

2806 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.065

S = 1.03

3224 reflections

199 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 2001 ▸); cell refinement: SAINT (Bruker, 2001 ▸); data reduction: SAINT; 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015011007/bq2399sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011007/bq2399Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015011007/bq2399Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015011007/bq2399fig1.tif

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.

Click here for additional data file.

. DOI: 10.1107/S2056989015011007/bq2399fig2.tif

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

CCDC reference: 1405247

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H14BrNO3S2	F(000) = 404
Mr = 400.30	Dx = 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

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

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(Fo2) + (0.0328P)2 + 0.2957P] where P = (Fo2 + 2Fc2)/3
3224 reflections	(Δ/σ)max = 0.001
199 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C17H17AO5i	0.97	2.53	3.501(2)	176
C17H17BS3	0.97	2.55	3.1633(16)	121
C19H19AS2	0.97	2.37	2.864(2)	111
C22H22BS3	0.97	2.61	3.0486(19)	108

Symmetry code: (i) .