(7-Chloro-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbodithio-ate.

In the title compound, C(16)H(16)ClNO(2)S(2), the piperidine ring is in a chair conformation. In the coumarin ring system, the dihedral angle between the benzene and pyran rings is 3.5 (1)°. In the crystal, a weak C-H⋯O hydrogen bond links mol-ecules into chains along [001]. In addition, π-π stacking inter-actions are present involving the benzene and pyran rings, with a centroid-to-centroid distance of 3.712 (2) Å. The crystal studied is a nonmerohedral twin with refined components 0.221 (1) and 0.779 (1).

Related literature

For structures and properties of coumarins, see: Kulkarni et al. (2006 ▶); Jones et al. (1985 ▶); Trenor et al. (2004 ▶); Hung et al. (2007 ▶). For the applications of dithio­carbamate compounds, see: Bergendorff & Hansson (2002 ▶); Huang et al. (2009 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For ring conformations, see: Duax & Norton (1975 ▶). For the synthesis of the title compound, see: Shastri et al. (2004 ▶); Vasilliev & Polackov (2000 ▶).

Experimental

Crystal data

C16H16ClNO2S2

M = 353.87

Monoclinic,

a = 4.9427 (3) Å

b = 11.5010 (6) Å

c = 14.0006 (8) Å

β = 90.271 (6)°

V = 795.87 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.51 mm−1

T = 293 K

0.3 × 0.2 × 0.2 mm

Data collection

Oxford Xcalibur Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T min = 0.886, T max = 1.000

13944 measured reflections

2801 independent reflections

2678 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.082

S = 1.04

2801 reflections

200 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.18 e Å−3

Absolute structure: Flack (1983 ▶), with 1394 Friedel pairs

Flack parameter: −0.01 (10)

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO ; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); 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: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812007933/lh5420sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007933/lh5420Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812007933/lh5420Isup3.cml

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

C16H16ClNO2S2	F(000) = 368
Mr = 353.87	Dx = 1.477 Mg m−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: p -2yc	Cell parameters from 7572 reflections
a = 4.9427 (3) Å	θ = 3.4–29.0°
b = 11.5010 (6) Å	µ = 0.51 mm−1
c = 14.0006 (8) Å	T = 293 K
β = 90.271 (6)°	Block, white
V = 795.87 (8) Å3	0.3 × 0.2 × 0.2 mm
Z = 2

Oxford Xcalibur Sapphire3 diffractometer	2801 independent reflections
Radiation source: fine-focus sealed tube	2678 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 16.1049 pixels mm-1	θmax = 25.0°, θmin = 3.4°
ω scans	h = −5→5
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −13→13
Tmin = 0.886, Tmax = 1.000	l = −16→16
13944 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035	H-atom parameters constrained
wR(F2) = 0.082	w = 1/[σ2(Fo2) + (0.0367P)2 + 0.3317P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
2801 reflections	Δρmax = 0.14 e Å−3
200 parameters	Δρmin = −0.18 e Å−3
2 restraints	Absolute structure: Flack (1983), with 1394 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.01 (10)

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

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 > σ(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	0.1990 (2)	0.77560 (7)	0.36977 (7)	0.0421 (3)
S2	0.4685 (3)	0.60142 (9)	0.24062 (9)	0.0525 (3)
Cl1	−0.4816 (2)	1.27262 (9)	0.15209 (9)	0.0577 (3)
O1	0.2148 (6)	0.9922 (2)	0.03114 (17)	0.0429 (7)
C2	0.4260 (9)	0.9155 (3)	0.0384 (3)	0.0431 (10)
O2	0.5440 (8)	0.8931 (3)	−0.03402 (19)	0.0583 (9)
C3	0.4925 (9)	0.8712 (3)	0.1330 (3)	0.0373 (9)
H3	0.6290	0.8161	0.1393	0.045*
C4	0.3622 (8)	0.9077 (3)	0.2120 (2)	0.0328 (8)
C10	0.1525 (8)	0.9952 (3)	0.2026 (2)	0.0315 (8)
C5	0.0142 (9)	1.0460 (3)	0.2788 (2)	0.0362 (8)
H5	0.0531	1.0225	0.3410	0.043*
C6	−0.1802 (9)	1.1309 (3)	0.2633 (3)	0.0405 (10)
H6	−0.2696	1.1644	0.3147	0.049*
C7	−0.2409 (8)	1.1657 (3)	0.1707 (3)	0.0372 (9)
C8	−0.1117 (9)	1.1168 (3)	0.0933 (3)	0.0385 (9)
H8	−0.1538	1.1396	0.0313	0.046*
C9	0.0813 (8)	1.0334 (3)	0.1108 (2)	0.0354 (9)
C11	0.4485 (9)	0.8620 (3)	0.3081 (3)	0.0382 (9)
H11B	0.4967	0.9276	0.3484	0.046*
H11A	0.6100	0.8153	0.2998	0.046*
C12	0.2473 (9)	0.6313 (3)	0.3254 (3)	0.0378 (9)
N1	0.0894 (7)	0.5538 (3)	0.3692 (3)	0.0487 (9)
C17	−0.0804 (10)	0.5754 (4)	0.4518 (4)	0.0538 (12)
H17A	−0.2672	0.5577	0.4360	0.065*
H17B	−0.0697	0.6569	0.4694	0.065*
C16	0.0100 (13)	0.5010 (4)	0.5353 (4)	0.0637 (12)
H16A	−0.1126	0.5127	0.5884	0.076*
H16B	0.1891	0.5253	0.5557	0.076*
C15	0.0164 (14)	0.3726 (4)	0.5096 (4)	0.0732 (16)
H15A	−0.1668	0.3446	0.4997	0.088*
H15B	0.0962	0.3287	0.5618	0.088*
C14	0.1810 (12)	0.3540 (4)	0.4192 (4)	0.0719 (17)
H14B	0.3697	0.3712	0.4323	0.086*
H14A	0.1684	0.2731	0.4000	0.086*
C13	0.0825 (11)	0.4303 (3)	0.3383 (4)	0.0609 (14)
H13A	0.1971	0.4198	0.2829	0.073*
H13B	−0.1008	0.4087	0.3207	0.073*

	U11	U22	U33	U12	U13	U23
S1	0.0626 (7)	0.0293 (5)	0.0344 (5)	0.0036 (5)	0.0134 (5)	0.0018 (4)
S2	0.0701 (7)	0.0446 (6)	0.0429 (5)	0.0132 (5)	0.0119 (6)	−0.0038 (5)
Cl1	0.0600 (7)	0.0446 (6)	0.0686 (8)	0.0118 (5)	0.0082 (6)	0.0067 (5)
O1	0.0627 (18)	0.0443 (16)	0.0218 (12)	0.0010 (14)	0.0080 (13)	−0.0001 (11)
C2	0.064 (3)	0.0350 (19)	0.031 (2)	−0.003 (2)	0.0083 (19)	−0.0062 (16)
O2	0.083 (2)	0.0600 (19)	0.0322 (16)	0.0051 (18)	0.0230 (17)	−0.0058 (13)
C3	0.048 (2)	0.0316 (18)	0.0324 (19)	−0.0030 (18)	0.0071 (19)	−0.0001 (15)
C4	0.041 (2)	0.0289 (18)	0.0287 (19)	−0.0076 (15)	0.0040 (15)	0.0011 (14)
C10	0.040 (2)	0.0283 (18)	0.0258 (19)	−0.0056 (16)	0.0035 (15)	0.0010 (14)
C5	0.050 (2)	0.0362 (19)	0.0224 (17)	−0.0096 (19)	0.0046 (16)	−0.0007 (14)
C6	0.053 (3)	0.034 (2)	0.035 (2)	−0.0039 (18)	0.0123 (18)	−0.0036 (16)
C7	0.040 (2)	0.0297 (19)	0.042 (2)	−0.0062 (16)	0.0032 (18)	0.0033 (16)
C8	0.051 (3)	0.034 (2)	0.0305 (19)	−0.0055 (18)	0.0035 (18)	0.0056 (16)
C9	0.050 (2)	0.0311 (18)	0.0255 (18)	−0.0070 (17)	0.0069 (16)	−0.0014 (14)
C11	0.050 (3)	0.0372 (18)	0.0272 (19)	0.0007 (18)	0.0024 (17)	−0.0029 (16)
C12	0.049 (2)	0.034 (2)	0.0302 (19)	0.0047 (18)	−0.0042 (18)	0.0013 (15)
N1	0.061 (2)	0.0286 (16)	0.056 (2)	0.0022 (15)	0.006 (2)	0.0004 (15)
C17	0.060 (3)	0.037 (2)	0.064 (3)	−0.001 (2)	0.013 (2)	0.009 (2)
C16	0.076 (3)	0.055 (3)	0.060 (3)	−0.005 (3)	−0.005 (3)	0.012 (2)
C15	0.087 (4)	0.044 (2)	0.088 (4)	−0.011 (3)	−0.029 (4)	0.023 (3)
C14	0.070 (4)	0.034 (2)	0.112 (5)	0.001 (2)	−0.028 (4)	−0.003 (3)
C13	0.077 (4)	0.031 (2)	0.075 (3)	−0.003 (2)	0.006 (3)	−0.008 (2)

S1—C12	1.788 (4)	C8—H8	0.9300
S1—C11	1.807 (4)	C11—H11B	0.9700
S2—C12	1.654 (4)	C11—H11A	0.9700
Cl1—C7	1.730 (4)	C12—N1	1.336 (5)
O1—C2	1.371 (5)	N1—C17	1.454 (5)
O1—C9	1.382 (4)	N1—C13	1.485 (5)
C2—O2	1.200 (4)	C17—C16	1.514 (6)
C2—C3	1.456 (5)	C17—H17A	0.9700
C3—C4	1.349 (5)	C17—H17B	0.9700
C3—H3	0.9300	C16—C15	1.521 (7)
C4—C10	1.450 (5)	C16—H16A	0.9700
C4—C11	1.505 (5)	C16—H16B	0.9700
C10—C5	1.398 (5)	C15—C14	1.524 (8)
C10—C9	1.402 (5)	C15—H15A	0.9700
C5—C6	1.386 (6)	C15—H15B	0.9700
C5—H5	0.9300	C14—C13	1.511 (7)
C6—C7	1.388 (5)	C14—H14B	0.9700
C6—H6	0.9300	C14—H14A	0.9700
C7—C8	1.380 (6)	C13—H13A	0.9700
C8—C9	1.374 (6)	C13—H13B	0.9700
C12—S1—C11	104.60 (18)	N1—C12—S1	112.4 (3)
C2—O1—C9	121.8 (3)	S2—C12—S1	122.2 (2)
O2—C2—O1	116.7 (4)	C12—N1—C17	126.3 (3)
O2—C2—C3	125.9 (4)	C12—N1—C13	121.2 (4)
O1—C2—C3	117.5 (3)	C17—N1—C13	112.5 (4)
C4—C3—C2	122.1 (4)	N1—C17—C16	110.4 (4)
C4—C3—H3	119.0	N1—C17—H17A	109.6
C2—C3—H3	119.0	C16—C17—H17A	109.6
C3—C4—C10	119.1 (3)	N1—C17—H17B	109.6
C3—C4—C11	119.3 (4)	C16—C17—H17B	109.6
C10—C4—C11	121.5 (3)	H17A—C17—H17B	108.1
C5—C10—C9	116.6 (3)	C17—C16—C15	111.8 (5)
C5—C10—C4	125.0 (3)	C17—C16—H16A	109.2
C9—C10—C4	118.5 (3)	C15—C16—H16A	109.2
C6—C5—C10	121.0 (3)	C17—C16—H16B	109.2
C6—C5—H5	119.5	C15—C16—H16B	109.2
C10—C5—H5	119.5	H16A—C16—H16B	107.9
C5—C6—C7	119.8 (4)	C16—C15—C14	110.2 (4)
C5—C6—H6	120.1	C16—C15—H15A	109.6
C7—C6—H6	120.1	C14—C15—H15A	109.6
C8—C7—C6	121.1 (4)	C16—C15—H15B	109.6
C8—C7—Cl1	119.5 (3)	C14—C15—H15B	109.6
C6—C7—Cl1	119.4 (3)	H15A—C15—H15B	108.1
C9—C8—C7	117.9 (4)	C13—C14—C15	111.7 (5)
C9—C8—H8	121.0	C13—C14—H14B	109.3
C7—C8—H8	121.0	C15—C14—H14B	109.3
C8—C9—O1	115.4 (3)	C13—C14—H14A	109.3
C8—C9—C10	123.6 (3)	C15—C14—H14A	109.3
O1—C9—C10	120.9 (3)	H14B—C14—H14A	107.9
C4—C11—S1	115.4 (3)	N1—C13—C14	109.3 (4)
C4—C11—H11B	108.4	N1—C13—H13A	109.8
S1—C11—H11B	108.4	C14—C13—H13A	109.8
C4—C11—H11A	108.4	N1—C13—H13B	109.8
S1—C11—H11A	108.4	C14—C13—H13B	109.8
H11B—C11—H11A	107.5	H13A—C13—H13B	108.3
N1—C12—S2	125.5 (3)
C9—O1—C2—O2	−173.5 (4)	C5—C10—C9—C8	0.5 (5)
C9—O1—C2—C3	4.7 (5)	C4—C10—C9—C8	−179.1 (4)
O2—C2—C3—C4	174.8 (4)	C5—C10—C9—O1	177.1 (3)
O1—C2—C3—C4	−3.2 (6)	C4—C10—C9—O1	−2.5 (5)
C2—C3—C4—C10	−1.1 (6)	C3—C4—C11—S1	−115.6 (4)
C2—C3—C4—C11	−177.6 (4)	C10—C4—C11—S1	68.0 (4)
C3—C4—C10—C5	−175.7 (4)	C12—S1—C11—C4	86.3 (3)
C11—C4—C10—C5	0.7 (5)	C11—S1—C12—N1	175.5 (3)
C3—C4—C10—C9	3.9 (5)	C11—S1—C12—S2	−3.6 (3)
C11—C4—C10—C9	−179.7 (3)	S2—C12—N1—C17	171.5 (4)
C9—C10—C5—C6	−0.9 (5)	S1—C12—N1—C17	−7.6 (5)
C4—C10—C5—C6	178.7 (4)	S2—C12—N1—C13	−5.4 (6)
C10—C5—C6—C7	0.5 (6)	S1—C12—N1—C13	175.4 (3)
C5—C6—C7—C8	0.3 (6)	C12—N1—C17—C16	−117.9 (5)
C5—C6—C7—Cl1	−179.4 (3)	C13—N1—C17—C16	59.3 (5)
C6—C7—C8—C9	−0.7 (6)	N1—C17—C16—C15	−55.2 (6)
Cl1—C7—C8—C9	179.0 (3)	C17—C16—C15—C14	52.2 (7)
C7—C8—C9—O1	−176.5 (3)	C16—C15—C14—C13	−53.3 (6)
C7—C8—C9—C10	0.3 (6)	C12—N1—C13—C14	117.5 (5)
C2—O1—C9—C8	175.0 (3)	C17—N1—C13—C14	−59.8 (6)
C2—O1—C9—C10	−1.9 (5)	C15—C14—C13—N1	56.3 (6)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17B···S1	0.97	2.36	2.923 (5)	116
C13—H13A···S2	0.97	2.55	3.067 (4)	113
C6—H6···O2i	0.93	2.41	3.167 (5)	139

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2i	0.93	2.41	3.167 (5)	139

Symmetry code: (i) .