(6-Meth­oxy-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbodi­thio­ate

Kumar, K.M.; Vinduvahini, M.; Mahabhaleshwaraiah, N.M.; Kotresh, O.; Devarajegowda, H.C.

doi:10.1107/S1600536813028432

organic compounds

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Volume 69| Part 11| November 2013| Page o1683

doi:10.1107/S1600536813028432

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(6-Methoxy-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbodithioate

K. Mahesh Kumar,^a M. Vinduvahini,^b N. M. Mahabhaleshwaraiah,^a O. Kotresh ^a and H. C. Devarajegowda ^c ^*

^aDepartment of Chemistry, Karnatak University's Karnatak Science College, Dharwad, Karnataka 580 001, India, ^bDepartment of Physics, Sri D Devaraja Urs Govt. First Grade College, Hunsur 571 105, Mysore District, Karnataka, India, and ^cDepartment of Physics, Yuvaraja's College (Constituent College), University of Mysore, Mysore 570 005, Karnataka, India
^*Correspondence e-mail: devarajegowda@yahoo.com

(Received 14 October 2013; accepted 16 October 2013; online 23 October 2013)

In the title compound, C₁₇H₁₉NO₃S₂, the maximum deviation of atoms in the 2H-chromene ring system is 0.0097 (14) Å and the piperidine ring adopts a chair conformation. The dihedral angle between the 2H-chromene ring and the piperidine ring (all atoms) is 87.59 (8)°. In the crystal, inversion dimers linked by pairs of C—H⋯O interactions generate R₂²(22) loops. Further C—H⋯O hydrogen bonds link the dimers into [110] chains and weak aromatic π–π stacking [shortest centroid–centroid distance = 3.824 (8) Å] is also observed.

CCDC reference: 966690

Related literature

For a related structure and the synthesis, see: Kumar et al. (2012 ).

Experimental

Crystal data

C₁₇H₁₉NO₃S₂
M_r = 349.45
Triclinic, $[P \overline 1]$
a = 6.9731 (2) Å
b = 10.2310 (3) Å
c = 11.9955 (3) Å
α = 92.024 (1)°
β = 90.176 (1)°
γ = 106.497 (1)°
V = 819.96 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.770, T_max = 1.000
17441 measured reflections
4261 independent reflections
3513 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.109
S = 1.04
4261 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19B⋯O5ⁱ	0.97	2.50	3.410 (2)	157
C23—H23A⋯O3ⁱⁱ	0.97	2.60	3.365 (2)	136
Symmetry codes: (i) -x, -y, -z+1; (ii) x-1, y-1, z.

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

CCDC reference: 966690

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813028432/hb7152sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813028432/hb7152Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813028432/hb7152Isup3.cml

checkCIF report

Comment top

As part of our ongoing structural studies of coumarin derivatives (Kumar et al., 2012), we now describe the title compound, (I) (Fig. 1).

The 2H- chromene ring system is almost planar, with a maximum deviation of 0.0097 (14) Å for atom C9 and the piperidine ring adopts a chair conformation. The dihedral angle between the 2H-chromene (O3/C7–C15) ring and the piperidine ring (N6/C19–C23) is 87.59 (8)°. In the crystal structure, C19—H19B···O5 and C23—H23A···O3 hydrogen bonding (Table 1) and π–π interactions between the fused benzene ring (C10–C15) of 2H-chromene and fused pyran ring (O3/C7–C11) [shortest centroid–centroid distance = 3.824 (8) Å] occur.

Related literature top

For a related structure and the synthesis, 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= 79%, m.p.395 K. IR (KBr) 655 cm^-1(C—S), 1243 cm^-1(C=S), 1006 cm^-1(C—O), 887 cm^-1 (C—N), 1161 cm^-1(C—O—C), 1719 cm^-1(C=O). GCMS: m/e: 349. 1H NMR (400 MHz, CDCl₃, \?, p.p.m.): 1.65(s, 6H, Piperidine-CH₂), 3.15(s, 3H, –OCH₃), 3.89(s, 2H, Piperidine-CH₂), 4.20(s, 2H Piperidine-CH₂), 4.70(d, 2H, Methylene-CH₂), 6.45(s, 1H, Ar—H), 7.14(d, 1H, Ar—H), 7.30(s, 1H, Ar—H), 7.50(s,1H, Ar—H). Elemental analysis for C₁₇H₁₉NO₃S₂: C, 58.36; H, 5.42; N, 3.93.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (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 piperidine-1-carbodithioate top

Crystal data top

C₁₇H₁₉NO₃S₂	F(000) = 368
M_r = 349.45	D_x = 1.415 Mg m⁻³
Triclinic, P1	Melting point: 395 K
a = 6.9731 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2310 (3) Å	Cell parameters from 4261 reflections
c = 11.9955 (3) Å	θ = 1.7–28.8°
α = 92.024 (1)°	µ = 0.34 mm⁻¹
β = 90.176 (1)°	T = 296 K
γ = 106.497 (1)°	Plate, colourless
V = 819.96 (4) Å³	0.24 × 0.20 × 0.12 mm
Z = 2

Data collection top

Bruker SMART CCD diffractometer	4261 independent reflections
Radiation source: fine-focus sealed tube	3513 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω and ϕ scans	θ_max = 28.8°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
T_min = 0.770, T_max = 1.000	k = −11→13
17441 measured reflections	l = −16→16

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.0576P)² + 0.1837P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4261 reflections	Δρ_max = 0.28 e Å⁻³
208 parameters	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₇H₁₉NO₃S₂	γ = 106.497 (1)°
M_r = 349.45	V = 819.96 (4) Å³
Triclinic, P1	Z = 2
a = 6.9731 (2) Å	Mo Kα radiation
b = 10.2310 (3) Å	µ = 0.34 mm⁻¹
c = 11.9955 (3) Å	T = 296 K
α = 92.024 (1)°	0.24 × 0.20 × 0.12 mm
β = 90.176 (1)°

Data collection top

Bruker SMART CCD diffractometer	4261 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	3513 reflections with I > 2σ(I)
T_min = 0.770, T_max = 1.000	R_int = 0.023
17441 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.04	Δρ_max = 0.28 e Å⁻³
4261 reflections	Δρ_min = −0.18 e Å⁻³
208 parameters

Special details top

Experimental. IR (KBr) 655 cm^-1(C—S), 1243 cm^-1(C=S), 1006 cm^-1(C—O), 887 cm^-1 (C—N), 1161 cm^-1(C—O—C), 1719 cm^-1(C=O). GCMS: m/e: 349. 1H NMR (400 MHz, CDCl₃, \?, p.p.m.): 1.65(s, 6H, Piperidine-CH₂), 3.15(s, 3H, –OCH₃), 3.89(s, 2H, Piperidine-CH₂), 4.20(s, 2H Piperidine-CH₂), 4.70(d, 2H, Methylene-CH₂), 6.45(s, 1H, Ar—H), 7.14(d, 1H, Ar—H), 7.30(s, 1H, Ar—H), 7.50(s,1H, Ar—H). Elemental analysis for C₁₇H₁₉NO₃S₂: C, 58.36; H, 5.42; N, 3.93.

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 > 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	−0.11287 (5)	0.07096 (4)	0.65164 (3)	0.04415 (12)
S2	0.27902 (6)	0.01452 (4)	0.70354 (4)	0.05410 (14)
O3	0.28766 (17)	0.60135 (11)	0.70830 (9)	0.0468 (3)
O4	0.2364 (2)	0.52695 (14)	0.87805 (10)	0.0691 (4)
O5	0.2788 (2)	0.51786 (12)	0.25306 (9)	0.0642 (4)
N6	−0.07603 (19)	−0.11995 (14)	0.78182 (12)	0.0498 (3)
C7	0.2257 (2)	0.49686 (16)	0.78009 (13)	0.0461 (3)
C8	0.1519 (2)	0.36058 (15)	0.73062 (12)	0.0417 (3)
H8	0.1090	0.2881	0.7778	0.050*
C9	0.14239 (19)	0.33355 (13)	0.62055 (11)	0.0348 (3)
C10	0.21349 (18)	0.44638 (13)	0.54632 (11)	0.0331 (3)
C11	0.2836 (2)	0.57753 (14)	0.59446 (11)	0.0366 (3)
C12	0.3533 (2)	0.69027 (14)	0.53032 (13)	0.0432 (3)
H12	0.3988	0.7768	0.5643	0.052*
C13	0.3553 (2)	0.67440 (14)	0.41558 (13)	0.0425 (3)
H13	0.4036	0.7500	0.3721	0.051*
C14	0.2849 (2)	0.54501 (15)	0.36542 (12)	0.0410 (3)
C15	0.2157 (2)	0.43231 (14)	0.43028 (11)	0.0380 (3)
H15	0.1700	0.3460	0.3960	0.046*
C16	0.3336 (3)	0.62831 (19)	0.18046 (14)	0.0585 (4)
H16A	0.3220	0.5938	0.1045	0.088*
H16B	0.4694	0.6806	0.1961	0.088*
H16C	0.2468	0.6854	0.1916	0.088*
C17	0.0638 (2)	0.19172 (14)	0.56997 (12)	0.0415 (3)
H17A	0.1767	0.1563	0.5551	0.050*
H17B	0.0011	0.1976	0.4988	0.050*
C18	0.0326 (2)	−0.02097 (14)	0.72018 (11)	0.0380 (3)
C19	0.0146 (3)	−0.20858 (17)	0.84504 (14)	0.0516 (4)
H19A	0.1589	−0.1777	0.8384	0.062*
H19B	−0.0318	−0.3013	0.8143	0.062*
C20	−0.0410 (3)	−0.2057 (2)	0.96626 (16)	0.0684 (5)
H20A	0.0082	−0.2715	1.0051	0.082*
H20B	0.0233	−0.1160	0.9995	0.082*
C21	−0.2638 (4)	−0.2379 (3)	0.98128 (18)	0.0868 (8)
H21A	−0.3259	−0.3330	0.9601	0.104*
H21B	−0.2915	−0.2246	1.0594	0.104*
C22	−0.3539 (3)	−0.1499 (2)	0.91250 (16)	0.0643 (5)
H22A	−0.3084	−0.0563	0.9413	0.077*
H22B	−0.4984	−0.1805	0.9179	0.077*
C23	−0.2955 (2)	−0.15637 (19)	0.79241 (15)	0.0540 (4)
H23A	−0.3544	−0.2479	0.7612	0.065*
H23B	−0.3471	−0.0940	0.7505	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0397 (2)	0.03896 (19)	0.0547 (2)	0.01085 (15)	0.00079 (15)	0.01674 (15)
S2	0.0365 (2)	0.0502 (2)	0.0774 (3)	0.01264 (17)	0.01009 (18)	0.0240 (2)
O3	0.0547 (6)	0.0401 (5)	0.0431 (5)	0.0095 (5)	−0.0055 (5)	0.0000 (4)
O4	0.0994 (11)	0.0649 (8)	0.0402 (6)	0.0193 (7)	−0.0079 (6)	−0.0026 (5)
O5	0.0992 (10)	0.0489 (7)	0.0404 (6)	0.0126 (6)	0.0149 (6)	0.0142 (5)
N6	0.0354 (6)	0.0536 (8)	0.0617 (8)	0.0112 (5)	0.0035 (5)	0.0300 (6)
C7	0.0487 (8)	0.0491 (8)	0.0412 (8)	0.0150 (7)	−0.0044 (6)	0.0037 (6)
C8	0.0443 (8)	0.0421 (7)	0.0403 (7)	0.0140 (6)	0.0002 (6)	0.0095 (6)
C9	0.0323 (6)	0.0349 (6)	0.0395 (7)	0.0126 (5)	0.0008 (5)	0.0081 (5)
C10	0.0286 (6)	0.0332 (6)	0.0399 (6)	0.0120 (5)	0.0011 (5)	0.0075 (5)
C11	0.0321 (6)	0.0367 (7)	0.0424 (7)	0.0114 (5)	−0.0018 (5)	0.0047 (5)
C12	0.0397 (7)	0.0326 (7)	0.0560 (8)	0.0075 (6)	−0.0037 (6)	0.0057 (6)
C13	0.0372 (7)	0.0364 (7)	0.0546 (8)	0.0100 (6)	0.0049 (6)	0.0163 (6)
C14	0.0397 (7)	0.0430 (7)	0.0424 (7)	0.0138 (6)	0.0066 (6)	0.0118 (6)
C15	0.0406 (7)	0.0336 (6)	0.0411 (7)	0.0121 (5)	0.0051 (5)	0.0073 (5)
C16	0.0623 (11)	0.0646 (11)	0.0490 (9)	0.0158 (9)	0.0132 (7)	0.0250 (8)
C17	0.0499 (8)	0.0344 (7)	0.0402 (7)	0.0109 (6)	0.0042 (6)	0.0102 (5)
C18	0.0385 (7)	0.0338 (6)	0.0416 (7)	0.0095 (5)	0.0008 (5)	0.0080 (5)
C19	0.0476 (9)	0.0489 (8)	0.0616 (9)	0.0161 (7)	0.0026 (7)	0.0253 (7)
C20	0.0691 (12)	0.0856 (14)	0.0536 (10)	0.0250 (11)	−0.0086 (9)	0.0175 (9)
C21	0.0761 (14)	0.133 (2)	0.0569 (11)	0.0354 (14)	0.0170 (10)	0.0390 (13)
C22	0.0486 (10)	0.0764 (13)	0.0676 (11)	0.0174 (9)	0.0071 (8)	0.0037 (9)
C23	0.0351 (7)	0.0615 (10)	0.0624 (10)	0.0061 (7)	0.0018 (7)	0.0264 (8)

Geometric parameters (Å, º) top

S1—C18	1.7837 (14)	C13—H13	0.9300
S1—C17	1.7980 (14)	C14—C15	1.3847 (18)
S2—C18	1.6662 (14)	C15—H15	0.9300
O3—C7	1.3697 (18)	C16—H16A	0.9600
O3—C11	1.3774 (17)	C16—H16B	0.9600
O4—C7	1.2008 (19)	C16—H16C	0.9600
O5—C14	1.3647 (18)	C17—H17A	0.9700
O5—C16	1.4169 (18)	C17—H17B	0.9700
N6—C18	1.3293 (17)	C19—C20	1.507 (3)
N6—C19	1.4722 (18)	C19—H19A	0.9700
N6—C23	1.4758 (19)	C19—H19B	0.9700
C7—C8	1.447 (2)	C20—C21	1.507 (3)
C8—C9	1.3370 (19)	C20—H20A	0.9700
C8—H8	0.9300	C20—H20B	0.9700
C9—C10	1.4565 (17)	C21—C22	1.502 (3)
C9—C17	1.503 (2)	C21—H21A	0.9700
C10—C11	1.3942 (19)	C21—H21B	0.9700
C10—C15	1.3949 (18)	C22—C23	1.502 (3)
C11—C12	1.3803 (19)	C22—H22A	0.9700
C12—C13	1.381 (2)	C22—H22B	0.9700
C12—H12	0.9300	C23—H23A	0.9700
C13—C14	1.389 (2)	C23—H23B	0.9700

C18—S1—C17	104.68 (7)	C9—C17—S1	116.29 (10)
C7—O3—C11	121.57 (11)	C9—C17—H17A	108.2
C14—O5—C16	118.89 (14)	S1—C17—H17A	108.2
C18—N6—C19	122.03 (13)	C9—C17—H17B	108.2
C18—N6—C23	125.13 (12)	S1—C17—H17B	108.2
C19—N6—C23	112.81 (12)	H17A—C17—H17B	107.4
O4—C7—O3	117.03 (15)	N6—C18—S2	124.86 (11)
O4—C7—C8	126.12 (15)	N6—C18—S1	113.21 (10)
O3—C7—C8	116.85 (13)	S2—C18—S1	121.91 (8)
C9—C8—C7	123.36 (13)	N6—C19—C20	110.31 (15)
C9—C8—H8	118.3	N6—C19—H19A	109.6
C7—C8—H8	118.3	C20—C19—H19A	109.6
C8—C9—C10	118.56 (12)	N6—C19—H19B	109.6
C8—C9—C17	122.94 (12)	C20—C19—H19B	109.6
C10—C9—C17	118.49 (11)	H19A—C19—H19B	108.1
C11—C10—C15	117.71 (12)	C21—C20—C19	112.10 (16)
C11—C10—C9	117.80 (12)	C21—C20—H20A	109.2
C15—C10—C9	124.49 (12)	C19—C20—H20A	109.2
O3—C11—C12	116.55 (12)	C21—C20—H20B	109.2
O3—C11—C10	121.83 (12)	C19—C20—H20B	109.2
C12—C11—C10	121.62 (13)	H20A—C20—H20B	107.9
C11—C12—C13	119.90 (13)	C22—C21—C20	112.04 (17)
C11—C12—H12	120.0	C22—C21—H21A	109.2
C13—C12—H12	120.0	C20—C21—H21A	109.2
C12—C13—C14	119.66 (12)	C22—C21—H21B	109.2
C12—C13—H13	120.2	C20—C21—H21B	109.2
C14—C13—H13	120.2	H21A—C21—H21B	107.9
O5—C14—C15	115.35 (13)	C21—C22—C23	110.75 (17)
O5—C14—C13	124.52 (12)	C21—C22—H22A	109.5
C15—C14—C13	120.13 (13)	C23—C22—H22A	109.5
C14—C15—C10	120.97 (13)	C21—C22—H22B	109.5
C14—C15—H15	119.5	C23—C22—H22B	109.5
C10—C15—H15	119.5	H22A—C22—H22B	108.1
O5—C16—H16A	109.5	N6—C23—C22	110.94 (14)
O5—C16—H16B	109.5	N6—C23—H23A	109.5
H16A—C16—H16B	109.5	C22—C23—H23A	109.5
O5—C16—H16C	109.5	N6—C23—H23B	109.5
H16A—C16—H16C	109.5	C22—C23—H23B	109.5
H16B—C16—H16C	109.5	H23A—C23—H23B	108.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19B···O5ⁱ	0.97	2.50	3.410 (2)	157
C23—H23A···O3ⁱⁱ	0.97	2.60	3.365 (2)	136

Symmetry codes: (i) −x, −y, −z+1; (ii) x−1, y−1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19B···O5ⁱ	0.97	2.50	3.410 (2)	157
C23—H23A···O3ⁱⁱ	0.97	2.60	3.365 (2)	136

Symmetry codes: (i) −x, −y, −z+1; (ii) x−1, y−1, z.

Acknowledgements

The authors thank the Universities Sophisticated Instrumental Centre, Karnatak University, Dharwad, for the CCD X-ray facilities, X-ray data collection, GCMS, IR, CHNS and NMR data. KMK is grateful to Karnatak Science College, Dharwad, for providing laboratory facilities.

References

Bruker (2007). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kumar, K. M., Kour, D., Kapoor, K., Mahabaleshwaraiah, N. M., Kotresh, O., Gupta, V. K. & Kant, R. (2012). Acta Cryst. E68, o878–o879. CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar