(7,8-Dimethyl-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbodi­thio­ate

Ravi, A.J.; Kumar, K.M.; Devarajegowda, H.C.

doi:10.1107/S2414314616001711

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 2| February 2016| x160171

https://doi.org/10.1107/S2414314616001711

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(7,8-Dimethyl-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbodithioate

A. J. Ravi,^a K. Mahesh Kumar ^b and H. C. Devarajegowda ^a ^*

^aDepartment of Physics, Yuvaraja's College (Constituent College), University of Mysore, Mysore 570 005, Karnataka, India, and ^bDepartment of Chemistry, Karnatak University's Karnatak Science College, Dharwad, Karnataka 580 001, India
^*Correspondence e-mail: devarajegowda@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 9 January 2016; accepted 27 January 2016; online 3 February 2016)

In the title compound, C₁₈H₂₁NO₂S₂, the 2H-chromene ring systems is nearly planar, with a maximum deviation of 0.023 (2) Å. The coumarin unit makes a dihedral angle of 60.54 (8)° with the piperidine ring, which adopts a chair conformation. The carbodithioate group is present in a synperiplanar conformation with respect to the piperidine ring, as indicated by the torsion angle of −4.7 (2)°. A short intramolecular C—H⋯S conatct generates an S(5) ring. No directional interactions beyond van der Waals contacts could be identified in the crystal.

Keywords: crystal structure; coumarin; piperidine; hydrogen bonding.

CCDC reference: 1450258

Structure description

As partof our onging structural studies of coumarin derivatives (Kumar et al., 2012 ; Anitha et al., 2016 ), we now describe the structure of the title compound.

The asymmetric unit is shown in Fig. 1. The 2H-chromene ring systems is nearly planar, with a maximum deviation of 0.0233 (20) Å for atom C10. The coumarin unit makes a dihedral angle of 60.54 (8)° with the mean plane of the piperidine ring. The carbodithioate group is present in a synperiplanar conformation with respect to the piperidine ring, as indicated by the torsion angle value of −4.7 (2)°. A short intramolecular C—H⋯S contact (Table 1) generates an S(5) ring. No directional interactions beyond van der Waals' contacts could be identified in the crystal.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17A⋯S2	0.97	2.45	3.134 (2)	127

Figure 1
Displacement ellipsoid plot of the title compound.

Synthesis and crystallization

The title compound was synthesized according to the reported method (Kumar et al., 2012). The compound was recrystallized from an ethanol–chloroform solvent mixture (v/v = 2/1) to yield colourless needles. Yield = 80%. m.p. 439–441, IR (KBr, cm⁻¹): 999, 1220, 1424, 1479, 1721. GCMS: m/e: 347. 1H NMR (400 MHz, CDCl₃, δ, p.p.m): d 7.03 (s, 1H, Ar—H), 6.92 (s, 1H, Ar—H), 6.53 (s, 1H, Ar—H), 4.80 (s, 2H, CH₂), 4.29 (s, 2H, CH₂), 3.90 (s, 2H, CH₂), 2.79 (s, 3H, CH₃), 2.38 (s, 3H, CH₃), 1.73 (m, 6H, CH₃). Mol. formula: C₁₈H₂₁NO₂S₂. Elemental analysis: C, 62.21; H, 6.09; N, 4.03 (calculated); C, 62.25; H, 6.04; N, 4.07 (found).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₂₁NO₂S₂
M_r	347.48
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.6767 (3), 16.2058 (3), 9.1417 (2)
β (°)	99.486 (2)
V (Å³)	1706.23 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.32
Crystal size (mm)	0.24 × 0.20 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.770, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	19606, 5070, 3111
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.711

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.140, 1.06
No. of reflections	5070
No. of parameters	208
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.18
Computer programs: SMART (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ).

Structural data

CCDC reference: 1450258

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616001711/hb4015sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616001711/hb4015Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616001711/hb4015Isup3.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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).

(7,8-Dimethyl-2-oxo-2H-chromen-4-yl)methyl piperidine-1-carbodithioate top

Crystal data top

C₁₈H₂₁NO₂S₂	D_x = 1.353 Mg m⁻³
M_r = 347.48	Melting point: 439 K
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.6767 (3) Å	Cell parameters from 5070 reflections
b = 16.2058 (3) Å	θ = 1.8–30.3°
c = 9.1417 (2) Å	µ = 0.32 mm⁻¹
β = 99.486 (2)°	T = 296 K
V = 1706.23 (7) Å³	Plate, colourless
Z = 4	0.24 × 0.20 × 0.12 mm
F(000) = 736

Data collection top

Bruker SMART CCD area-detector diffractometer	5070 independent reflections
Radiation source: fine-focus sealed tube	3111 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω and φ scans	θ_max = 30.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→16
T_min = 0.770, T_max = 1.000	k = −22→22
19606 measured reflections	l = −11→12

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.140	w = 1/[σ²(F_o²) + (0.0649P)² + 0.1225P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
5070 reflections	Δρ_max = 0.29 e Å⁻³
208 parameters	Δρ_min = −0.18 e Å⁻³

Special details top

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

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

	x	y	z	U_iso*/U_eq
S1	0.72757 (4)	0.85043 (3)	0.04750 (6)	0.05596 (17)
S2	0.97470 (5)	0.86854 (3)	0.20673 (7)	0.06158 (18)
O3	0.52322 (11)	1.12401 (7)	0.20252 (15)	0.0522 (3)
O4	0.43238 (14)	1.02016 (9)	0.2869 (2)	0.0849 (5)
N5	0.85029 (13)	0.73033 (9)	0.18090 (18)	0.0505 (4)
C6	0.52787 (18)	1.29307 (12)	0.1852 (3)	0.0624 (5)
H6A	0.4757	1.2581	0.2278	0.094*
H6B	0.5689	1.3282	0.2607	0.094*
H6C	0.4844	1.3263	0.1085	0.094*
C7	0.7133 (2)	1.36691 (12)	0.0386 (3)	0.0676 (6)
H7A	0.7770	1.3786	−0.0125	0.101*
H7B	0.6433	1.3901	−0.0157	0.101*
H7C	0.7285	1.3907	0.1361	0.101*
C8	0.69952 (16)	1.27483 (11)	0.0510 (2)	0.0502 (4)
C9	0.77554 (17)	1.22298 (12)	−0.0077 (2)	0.0560 (5)
H9	0.8318	1.2462	−0.0562	0.067*
C10	0.77018 (16)	1.13909 (11)	0.0036 (2)	0.0500 (4)
H10	0.8223	1.1062	−0.0368	0.060*
C11	0.68595 (14)	1.10240 (10)	0.07637 (19)	0.0419 (4)
C12	0.60991 (14)	1.15510 (10)	0.13132 (19)	0.0419 (4)
C13	0.61317 (15)	1.24084 (11)	0.1205 (2)	0.0456 (4)
C14	0.67517 (14)	1.01447 (10)	0.0980 (2)	0.0438 (4)
C15	0.59226 (16)	0.98717 (11)	0.1716 (2)	0.0511 (4)
H15	0.5870	0.9308	0.1884	0.061*
C16	0.51136 (17)	1.04126 (12)	0.2253 (2)	0.0547 (5)
C17	0.75634 (18)	0.95856 (11)	0.0327 (2)	0.0565 (5)
H17A	0.8351	0.9695	0.0817	0.068*
H17B	0.7522	0.9723	−0.0713	0.068*
C18	0.85766 (15)	0.81038 (11)	0.15314 (18)	0.0440 (4)
C19	0.95023 (19)	0.68230 (13)	0.2544 (2)	0.0607 (5)
H19A	0.9315	0.6568	0.3435	0.073*
H19B	1.0163	0.7185	0.2827	0.073*
C20	0.98043 (19)	0.61655 (13)	0.1501 (3)	0.0673 (6)
H20A	1.0057	0.6425	0.0653	0.081*
H20B	1.0441	0.5834	0.2005	0.081*
C21	0.8778 (2)	0.56170 (13)	0.0977 (3)	0.0731 (7)
H21A	0.8587	0.5304	0.1808	0.088*
H21B	0.8976	0.5230	0.0249	0.088*
C22	0.77386 (19)	0.61218 (12)	0.0296 (2)	0.0609 (5)
H22A	0.7893	0.6376	−0.0612	0.073*
H22B	0.7070	0.5763	0.0047	0.073*
C23	0.74742 (16)	0.67820 (11)	0.1354 (2)	0.0533 (5)
H23A	0.6834	0.7120	0.0876	0.064*
H23B	0.7245	0.6527	0.2221	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0489 (3)	0.0383 (3)	0.0793 (4)	0.00565 (19)	0.0064 (2)	−0.0011 (2)
S2	0.0517 (3)	0.0575 (3)	0.0752 (4)	−0.0109 (2)	0.0093 (3)	−0.0097 (2)
O3	0.0466 (7)	0.0446 (7)	0.0696 (9)	0.0051 (5)	0.0225 (6)	0.0014 (6)
O4	0.0832 (11)	0.0629 (10)	0.1247 (14)	−0.0001 (8)	0.0649 (11)	0.0065 (9)
N5	0.0483 (9)	0.0424 (8)	0.0579 (10)	0.0004 (6)	0.0000 (7)	−0.0011 (7)
C6	0.0590 (13)	0.0456 (11)	0.0829 (15)	0.0110 (9)	0.0125 (11)	−0.0083 (10)
C7	0.0735 (15)	0.0421 (11)	0.0856 (16)	−0.0061 (10)	0.0086 (13)	0.0034 (10)
C8	0.0484 (10)	0.0398 (10)	0.0593 (12)	−0.0009 (8)	0.0001 (9)	0.0008 (8)
C9	0.0506 (11)	0.0480 (11)	0.0719 (13)	−0.0061 (8)	0.0174 (10)	0.0064 (9)
C10	0.0431 (10)	0.0471 (10)	0.0623 (12)	0.0029 (8)	0.0163 (9)	0.0026 (8)
C11	0.0381 (9)	0.0385 (9)	0.0487 (10)	0.0030 (7)	0.0062 (7)	0.0021 (7)
C12	0.0367 (9)	0.0405 (9)	0.0483 (10)	0.0012 (7)	0.0064 (7)	0.0017 (7)
C13	0.0414 (9)	0.0410 (9)	0.0524 (10)	0.0033 (7)	0.0015 (8)	−0.0032 (7)
C14	0.0428 (9)	0.0365 (9)	0.0519 (10)	0.0040 (7)	0.0073 (8)	0.0021 (7)
C15	0.0521 (11)	0.0401 (9)	0.0638 (12)	0.0014 (8)	0.0181 (9)	0.0054 (8)
C16	0.0519 (11)	0.0471 (10)	0.0688 (13)	−0.0009 (8)	0.0212 (10)	0.0031 (9)
C17	0.0575 (12)	0.0383 (10)	0.0786 (14)	0.0069 (8)	0.0260 (10)	0.0031 (9)
C18	0.0459 (10)	0.0450 (10)	0.0428 (10)	0.0024 (7)	0.0126 (8)	−0.0070 (7)
C19	0.0600 (12)	0.0545 (12)	0.0633 (13)	0.0082 (9)	−0.0025 (10)	0.0071 (10)
C20	0.0577 (13)	0.0602 (13)	0.0856 (16)	0.0086 (10)	0.0169 (11)	0.0068 (11)
C21	0.0715 (15)	0.0473 (12)	0.1060 (19)	0.0015 (10)	0.0307 (14)	−0.0117 (11)
C22	0.0647 (13)	0.0533 (12)	0.0672 (13)	−0.0136 (10)	0.0182 (11)	−0.0062 (10)
C23	0.0498 (11)	0.0409 (9)	0.0695 (13)	−0.0025 (8)	0.0104 (10)	0.0029 (9)

Geometric parameters (Å, º) top

S1—C18	1.7825 (18)	C11—C12	1.385 (2)
S1—C17	1.7937 (18)	C11—C14	1.447 (2)
S2—C18	1.6660 (18)	C12—C13	1.394 (2)
O3—C16	1.368 (2)	C14—C15	1.342 (2)
O3—C12	1.385 (2)	C14—C17	1.504 (2)
O4—C16	1.206 (2)	C15—C16	1.434 (2)
N5—C18	1.327 (2)	C15—H15	0.9300
N5—C19	1.470 (2)	C17—H17A	0.9700
N5—C23	1.471 (2)	C17—H17B	0.9700
C6—C13	1.501 (2)	C19—C20	1.510 (3)
C6—H6A	0.9600	C19—H19A	0.9700
C6—H6B	0.9600	C19—H19B	0.9700
C6—H6C	0.9600	C20—C21	1.506 (3)
C7—C8	1.507 (3)	C20—H20A	0.9700
C7—H7A	0.9600	C20—H20B	0.9700
C7—H7B	0.9600	C21—C22	1.510 (3)
C7—H7C	0.9600	C21—H21A	0.9700
C8—C13	1.391 (3)	C21—H21B	0.9700
C8—C9	1.392 (3)	C22—C23	1.508 (3)
C9—C10	1.366 (3)	C22—H22A	0.9700
C9—H9	0.9300	C22—H22B	0.9700
C10—C11	1.407 (2)	C23—H23A	0.9700
C10—H10	0.9300	C23—H23B	0.9700

C18—S1—C17	104.07 (9)	O4—C16—C15	125.74 (18)
C16—O3—C12	121.90 (14)	O3—C16—C15	117.27 (15)
C18—N5—C19	122.23 (16)	C14—C17—S1	114.87 (13)
C18—N5—C23	125.64 (15)	C14—C17—H17A	108.5
C19—N5—C23	112.02 (15)	S1—C17—H17A	108.5
C13—C6—H6A	109.5	C14—C17—H17B	108.5
C13—C6—H6B	109.5	S1—C17—H17B	108.5
H6A—C6—H6B	109.5	H17A—C17—H17B	107.5
C13—C6—H6C	109.5	N5—C18—S2	124.93 (14)
H6A—C6—H6C	109.5	N5—C18—S1	112.53 (13)
H6B—C6—H6C	109.5	S2—C18—S1	122.54 (11)
C8—C7—H7A	109.5	N5—C19—C20	109.61 (17)
C8—C7—H7B	109.5	N5—C19—H19A	109.7
H7A—C7—H7B	109.5	C20—C19—H19A	109.7
C8—C7—H7C	109.5	N5—C19—H19B	109.7
H7A—C7—H7C	109.5	C20—C19—H19B	109.7
H7B—C7—H7C	109.5	H19A—C19—H19B	108.2
C13—C8—C9	119.55 (16)	C21—C20—C19	111.18 (18)
C13—C8—C7	121.40 (17)	C21—C20—H20A	109.4
C9—C8—C7	119.05 (18)	C19—C20—H20A	109.4
C10—C9—C8	122.10 (17)	C21—C20—H20B	109.4
C10—C9—H9	118.9	C19—C20—H20B	109.4
C8—C9—H9	118.9	H20A—C20—H20B	108.0
C9—C10—C11	120.07 (17)	C20—C21—C22	110.78 (17)
C9—C10—H10	120.0	C20—C21—H21A	109.5
C11—C10—H10	120.0	C22—C21—H21A	109.5
C12—C11—C10	116.80 (15)	C20—C21—H21B	109.5
C12—C11—C14	118.84 (15)	C22—C21—H21B	109.5
C10—C11—C14	124.35 (15)	H21A—C21—H21B	108.1
C11—C12—O3	120.53 (15)	C23—C22—C21	110.82 (18)
C11—C12—C13	124.22 (16)	C23—C22—H22A	109.5
O3—C12—C13	115.24 (14)	C21—C22—H22A	109.5
C8—C13—C12	117.23 (16)	C23—C22—H22B	109.5
C8—C13—C6	122.32 (17)	C21—C22—H22B	109.5
C12—C13—C6	120.44 (16)	H22A—C22—H22B	108.1
C15—C14—C11	118.65 (15)	N5—C23—C22	110.17 (15)
C15—C14—C17	123.66 (16)	N5—C23—H23A	109.6
C11—C14—C17	117.67 (15)	C22—C23—H23A	109.6
C14—C15—C16	122.75 (17)	N5—C23—H23B	109.6
C14—C15—H15	118.6	C22—C23—H23B	109.6
C16—C15—H15	118.6	H23A—C23—H23B	108.1
O4—C16—O3	116.98 (17)

C13—C8—C9—C10	−1.6 (3)	C11—C14—C15—C16	2.2 (3)
C7—C8—C9—C10	178.0 (2)	C17—C14—C15—C16	−176.22 (19)
C8—C9—C10—C11	0.0 (3)	C12—O3—C16—O4	−179.19 (18)
C9—C10—C11—C12	1.2 (3)	C12—O3—C16—C15	−0.4 (3)
C9—C10—C11—C14	−178.15 (19)	C14—C15—C16—O4	176.9 (2)
C10—C11—C12—O3	179.04 (16)	C14—C15—C16—O3	−1.8 (3)
C14—C11—C12—O3	−1.6 (3)	C15—C14—C17—S1	4.6 (3)
C10—C11—C12—C13	−0.9 (3)	C11—C14—C17—S1	−173.78 (14)
C14—C11—C12—C13	178.49 (17)	C18—S1—C17—C14	−119.89 (15)
C16—O3—C12—C11	2.0 (3)	C19—N5—C18—S2	−4.7 (2)
C16—O3—C12—C13	−178.05 (17)	C23—N5—C18—S2	179.53 (14)
C9—C8—C13—C12	1.9 (3)	C19—N5—C18—S1	174.31 (14)
C7—C8—C13—C12	−177.70 (18)	C23—N5—C18—S1	−1.5 (2)
C9—C8—C13—C6	−179.57 (18)	C17—S1—C18—N5	177.30 (13)
C7—C8—C13—C6	0.9 (3)	C17—S1—C18—S2	−3.67 (13)
C11—C12—C13—C8	−0.6 (3)	C18—N5—C19—C20	−116.9 (2)
O3—C12—C13—C8	179.44 (16)	C23—N5—C19—C20	59.4 (2)
C11—C12—C13—C6	−179.25 (18)	N5—C19—C20—C21	−56.5 (2)
O3—C12—C13—C6	0.8 (3)	C19—C20—C21—C22	54.5 (3)
C12—C11—C14—C15	−0.5 (3)	C20—C21—C22—C23	−54.1 (3)
C10—C11—C14—C15	178.87 (18)	C18—N5—C23—C22	116.7 (2)
C12—C11—C14—C17	178.01 (17)	C19—N5—C23—C22	−59.4 (2)
C10—C11—C14—C17	−2.7 (3)	C21—C22—C23—N5	55.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17A···S2	0.97	2.45	3.134 (2)	127

Acknowledgements

The authors thank the Universities Sophisticated Instrumental Centre, Karnatak University, Dharwad, for the X-ray data collection.

References

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