(6-Meth-oxy-2-oxo-2H-chromen-4-yl)methyl pyrrolidine-1-carbodithio-ate.

In the title compound, C(16)H(17)NO(3)S(2), the 2H-chromene ring is close to being planar [maximum deviation = 0.034 (2) Å] and the pyrrolidine ring is twisted about the C-C bond opposite the N atom. The dihedral angle between the ring-system planes is 75.24 (16)° and an intra-molecular C-H⋯S inter-action occurs. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds and the packing also exhibits π-π inter-actions, with a distance of 3.6106 (13) Å between the centroids of the benzene rings of neighbouring mol-ecules.

Related literature

For a related structure and background to the properties of coumarins, see: Kant et al. (2012 ▶). For further synthetic details, see: Shastri et al. (2004 ▶); Vasilliev et al. (2000 ▶).

Experimental

Crystal data

C16H17NO3S2

M = 335.43

Triclinic,

a = 6.7223 (2) Å

b = 8.0369 (2) Å

c = 15.4101 (5) Å

α = 75.320 (2)°

β = 88.482 (1)°

γ = 78.842 (1)°

V = 789.93 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.35 mm−1

T = 293 K

0.24 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.770, T max = 1.000

15231 measured reflections

2768 independent reflections

2453 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.128

S = 1.05

2768 reflections

200 parameters

H-atom parameters constrained

Δρmax = 0.51 e Å−3

Δρmin = −0.27 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: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812017953/hb6751sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017953/hb6751Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812017953/hb6751Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H17NO3S2	Z = 2
Mr = 335.43	F(000) = 352
Triclinic, P1	Dx = 1.410 Mg m−3
Hall symbol: -P 1	Melting point: 435 K
a = 6.7223 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.0369 (2) Å	Cell parameters from 2768 reflections
c = 15.4101 (5) Å	θ = 2.7–25.0°
α = 75.320 (2)°	µ = 0.35 mm−1
β = 88.482 (1)°	T = 293 K
γ = 78.842 (1)°	Plate, colourless
V = 789.93 (4) Å3	0.24 × 0.20 × 0.12 mm

Bruker SMART CCD diffractometer	2768 independent reflections
Radiation source: fine-focus sealed tube	2453 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω and φ scans	θmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→7
Tmin = 0.770, Tmax = 1.000	k = −9→9
15231 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0674P)2 + 0.3732P] where P = (Fo2 + 2Fc2)/3
2768 reflections	(Δ/σ)max < 0.001
200 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.19010 (9)	0.10311 (9)	0.13745 (4)	0.0584 (2)
S2	0.60578 (10)	0.18643 (10)	0.08087 (5)	0.0710 (2)
O3	−0.3276 (3)	−0.0847 (2)	0.41586 (13)	0.0658 (5)
O4	0.1152 (3)	0.4294 (2)	0.39350 (11)	0.0574 (4)
O5	0.3545 (4)	0.5741 (3)	0.34066 (16)	0.0881 (6)
N6	0.2772 (3)	0.2620 (2)	−0.02227 (13)	0.0522 (5)
C7	−0.2661 (5)	−0.2251 (3)	0.3765 (2)	0.0716 (7)
H7A	−0.2656	−0.1814	0.3124	0.107*
H7B	−0.3585	−0.3048	0.3919	0.107*
H7C	−0.1321	−0.2852	0.3980	0.107*
C8	−0.2095 (3)	0.0380 (3)	0.40578 (15)	0.0495 (5)
C9	−0.0408 (3)	0.0425 (3)	0.35217 (14)	0.0471 (5)
H9	−0.0035	−0.0412	0.3197	0.057*
C10	0.0731 (3)	0.1724 (3)	0.34692 (13)	0.0434 (5)
C11	0.0111 (4)	0.2970 (3)	0.39567 (14)	0.0473 (5)
C12	−0.1572 (4)	0.2920 (3)	0.44935 (15)	0.0540 (6)
H12	−0.1956	0.3754	0.4820	0.065*
C13	−0.2659 (4)	0.1638 (3)	0.45391 (15)	0.0545 (6)
H13	−0.3794	0.1603	0.4897	0.065*
C14	0.2545 (3)	0.1843 (3)	0.29518 (14)	0.0471 (5)
C15	0.3517 (4)	0.3155 (3)	0.29444 (16)	0.0572 (6)
H15	0.4696	0.3210	0.2618	0.069*
C16	0.2814 (4)	0.4486 (3)	0.34202 (17)	0.0610 (6)
C17	0.3306 (4)	0.0515 (3)	0.24279 (15)	0.0546 (6)
H17A	0.3167	−0.0640	0.2780	0.066*
H17B	0.4734	0.0496	0.2309	0.066*
C18	0.3634 (3)	0.1932 (3)	0.05759 (16)	0.0493 (5)
C19	0.0669 (4)	0.2655 (4)	−0.04648 (18)	0.0676 (7)
H19A	−0.0266	0.3443	−0.0191	0.081*
H19B	0.0347	0.1493	−0.0275	0.081*
C20	0.0557 (6)	0.3305 (6)	−0.1473 (2)	0.1022 (12)
H20A	0.0747	0.2328	−0.1749	0.123*
H20B	−0.0747	0.4054	−0.1670	0.123*
C21	0.2206 (6)	0.4298 (5)	−0.1712 (2)	0.0920 (10)
H21A	0.1743	0.5511	−0.1698	0.110*
H21B	0.2682	0.4266	−0.2309	0.110*
C22	0.3867 (5)	0.3409 (4)	−0.10192 (18)	0.0695 (7)
H22A	0.4816	0.2516	−0.1219	0.083*
H22B	0.4600	0.4251	−0.0891	0.083*

	U11	U22	U33	U12	U13	U23
S1	0.0516 (4)	0.0805 (4)	0.0513 (3)	−0.0254 (3)	0.0134 (3)	−0.0233 (3)
S2	0.0432 (4)	0.0889 (5)	0.0828 (5)	−0.0197 (3)	0.0108 (3)	−0.0209 (4)
O3	0.0625 (11)	0.0579 (10)	0.0844 (12)	−0.0230 (8)	0.0155 (9)	−0.0240 (9)
O4	0.0653 (11)	0.0497 (9)	0.0624 (10)	−0.0165 (8)	0.0038 (8)	−0.0199 (7)
O5	0.0919 (15)	0.0733 (12)	0.1171 (17)	−0.0450 (11)	0.0114 (13)	−0.0359 (12)
N6	0.0517 (11)	0.0552 (11)	0.0534 (11)	−0.0160 (8)	0.0119 (8)	−0.0175 (9)
C7	0.0665 (17)	0.0551 (14)	0.099 (2)	−0.0158 (12)	−0.0006 (15)	−0.0272 (14)
C8	0.0487 (13)	0.0462 (11)	0.0509 (12)	−0.0090 (9)	0.0005 (10)	−0.0075 (9)
C9	0.0518 (13)	0.0424 (11)	0.0473 (11)	−0.0075 (9)	0.0025 (9)	−0.0132 (9)
C10	0.0484 (12)	0.0408 (10)	0.0369 (10)	−0.0040 (9)	−0.0026 (8)	−0.0054 (8)
C11	0.0553 (13)	0.0415 (11)	0.0442 (11)	−0.0092 (9)	−0.0033 (9)	−0.0090 (9)
C12	0.0631 (15)	0.0511 (12)	0.0474 (12)	−0.0040 (11)	0.0057 (10)	−0.0177 (10)
C13	0.0551 (14)	0.0547 (13)	0.0515 (12)	−0.0088 (11)	0.0102 (10)	−0.0121 (10)
C14	0.0474 (12)	0.0462 (11)	0.0444 (11)	−0.0082 (9)	−0.0024 (9)	−0.0060 (9)
C15	0.0522 (14)	0.0604 (14)	0.0595 (14)	−0.0175 (11)	0.0047 (11)	−0.0117 (11)
C16	0.0641 (16)	0.0542 (13)	0.0669 (15)	−0.0193 (12)	−0.0062 (12)	−0.0128 (11)
C17	0.0499 (13)	0.0567 (13)	0.0545 (13)	−0.0064 (10)	0.0067 (10)	−0.0124 (10)
C18	0.0462 (13)	0.0469 (11)	0.0611 (13)	−0.0122 (9)	0.0137 (10)	−0.0237 (10)
C19	0.0595 (16)	0.0845 (18)	0.0611 (15)	−0.0181 (13)	0.0014 (12)	−0.0194 (13)
C20	0.105 (3)	0.130 (3)	0.0654 (19)	−0.038 (2)	−0.0115 (18)	0.0000 (19)
C21	0.120 (3)	0.095 (2)	0.0615 (17)	−0.038 (2)	0.0020 (18)	−0.0095 (16)
C22	0.0791 (19)	0.0671 (15)	0.0659 (16)	−0.0263 (14)	0.0254 (14)	−0.0168 (13)

S1—C18	1.787 (2)	C12—C13	1.361 (3)
S1—C17	1.813 (2)	C12—H12	0.9300
S2—C18	1.666 (2)	C13—H13	0.9300
O3—C8	1.358 (3)	C14—C15	1.341 (3)
O3—C7	1.403 (3)	C14—C17	1.502 (3)
O4—C16	1.364 (3)	C15—C16	1.446 (4)
O4—C11	1.375 (3)	C15—H15	0.9300
O5—C16	1.199 (3)	C17—H17A	0.9700
N6—C18	1.313 (3)	C17—H17B	0.9700
N6—C19	1.465 (3)	C19—C20	1.507 (4)
N6—C22	1.480 (3)	C19—H19A	0.9700
C7—H7A	0.9600	C19—H19B	0.9700
C7—H7B	0.9600	C20—C21	1.474 (5)
C7—H7C	0.9600	C20—H20A	0.9700
C8—C9	1.386 (3)	C20—H20B	0.9700
C8—C13	1.391 (3)	C21—C22	1.505 (5)
C9—C10	1.395 (3)	C21—H21A	0.9700
C9—H9	0.9300	C21—H21B	0.9700
C10—C11	1.395 (3)	C22—H22A	0.9700
C10—C14	1.445 (3)	C22—H22B	0.9700
C11—C12	1.385 (3)
C18—S1—C17	102.70 (11)	O5—C16—O4	116.9 (2)
C8—O3—C7	118.4 (2)	O5—C16—C15	126.6 (3)
C16—O4—C11	121.98 (18)	O4—C16—C15	116.5 (2)
C18—N6—C19	126.0 (2)	C14—C17—S1	110.94 (16)
C18—N6—C22	123.3 (2)	C14—C17—H17A	109.5
C19—N6—C22	110.6 (2)	S1—C17—H17A	109.5
O3—C7—H7A	109.5	C14—C17—H17B	109.5
O3—C7—H7B	109.5	S1—C17—H17B	109.5
H7A—C7—H7B	109.5	H17A—C17—H17B	108.0
O3—C7—H7C	109.5	N6—C18—S2	124.10 (18)
H7A—C7—H7C	109.5	N6—C18—S1	111.67 (17)
H7B—C7—H7C	109.5	S2—C18—S1	124.21 (15)
O3—C8—C9	124.1 (2)	N6—C19—C20	104.6 (2)
O3—C8—C13	115.9 (2)	N6—C19—H19A	110.8
C9—C8—C13	119.9 (2)	C20—C19—H19A	110.8
C8—C9—C10	120.1 (2)	N6—C19—H19B	110.8
C8—C9—H9	120.0	C20—C19—H19B	110.8
C10—C9—H9	120.0	H19A—C19—H19B	108.9
C11—C10—C9	118.4 (2)	C21—C20—C19	105.7 (3)
C11—C10—C14	117.6 (2)	C21—C20—H20A	110.6
C9—C10—C14	123.99 (19)	C19—C20—H20A	110.6
O4—C11—C12	116.88 (19)	C21—C20—H20B	110.6
O4—C11—C10	121.7 (2)	C19—C20—H20B	110.6
C12—C11—C10	121.4 (2)	H20A—C20—H20B	108.7
C13—C12—C11	119.3 (2)	C20—C21—C22	105.6 (3)
C13—C12—H12	120.3	C20—C21—H21A	110.6
C11—C12—H12	120.3	C22—C21—H21A	110.6
C12—C13—C8	120.9 (2)	C20—C21—H21B	110.6
C12—C13—H13	119.6	C22—C21—H21B	110.6
C8—C13—H13	119.6	H21A—C21—H21B	108.8
C15—C14—C10	119.0 (2)	N6—C22—C21	103.7 (2)
C15—C14—C17	121.1 (2)	N6—C22—H22A	111.0
C10—C14—C17	119.93 (19)	C21—C22—H22A	111.0
C14—C15—C16	123.0 (2)	N6—C22—H22B	111.0
C14—C15—H15	118.5	C21—C22—H22B	111.0
C16—C15—H15	118.5	H22A—C22—H22B	109.0

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O5i	0.96	2.55	3.396 (4)	147
C7—H7C···O4ii	0.96	2.57	3.356 (3)	139
C13—H13···O3iii	0.93	2.50	3.411 (3)	168
C17—H17B···S2	0.97	2.52	3.160 (3)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7B⋯O5i	0.96	2.55	3.396 (4)	147
C7—H7C⋯O4ii	0.96	2.57	3.356 (3)	139
C13—H13⋯O3iii	0.93	2.50	3.411 (3)	168
C17—H17B⋯S2	0.97	2.52	3.160 (3)	124

Symmetry codes: (i) ; (ii) ; (iii) .