(3-Oxo-3H-benzo[f]chromen-1-yl)methyl N,N-dimethyl­carbamodithio­ate

Abstract

In the title compound, C₁₇H₁₅NO₂S₂, the 3H-benzo[f]chromene ring system is distinctly twisted; the dihedral angle between the pyran ring and its opposite benzene ring is 9.11 (8)°. The N,N-dimethyl­carbamodithio­ate residue lies almost perpendicular to the pyran ring [dihedral angle = 85.15 (7)°]. In the crystal, weak C—H⋯O hydrogen bonds link the mol­ecules into C(10) chains propagating in [001].

Related literature  

For a related structure and background to coumarins, see: Kant et al. (2012 ▶); For the synthesis of the title compound, see: Kumar et al. (2012 ▶).

Experimental  

Crystal data  

• C₁₇H₁₅NO₂S₂

• M _r = 329.42

• Monoclinic,

• a = 14.1575 (2) Å

• b = 6.9399 (1) Å

• c = 15.9750 (2) Å

• β = 101.591 (1)°

• V = 1537.56 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.35 mm⁻¹

• T = 296 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

• 14561 measured reflections

• 2708 independent reflections

• 2387 reflections with I > 2σ(I)

• R _int = 0.023

Refinement  

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.104

• S = 1.06

• 2708 reflections

• 199 parameters

• H-atom parameters constrained

• Δρ_max = 0.28 e Å⁻³

• Δρ_min = −0.24 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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S160053681203975X/hb6942Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2i	0.93	2.51	3.405 (3)	162

Symmetry code: (i) .

supplementary crystallographic information

Experimental

The title compound was synthesized according to the reported method (Kumar et al., 2012). It was recrystallized from an ethanol–chloroform solvent mixture as colourless plates. Yield = 81%, m.p. 435 K.

Refinement

All H atoms were positioned geometrically, with C—H = 0.93 Å for aromatic H, C—H = 0.97 Å for methylene H and C—H = 0.96 Å for methyl H, and refined using a riding model with U_iso(H) = 1.5U_eq(C) for methyl H and U_iso(H) = 1.2U_eq(C) for all other H.

Figures

Fig. 1.

The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The H atoms are shown as spheres of arbitrary radii.

Fig. 2.

Packing of the molecules.

Crystal data

C17H15NO2S2	F(000) = 688
Mr = 329.42	Dx = 1.423 Mg m−3
Monoclinic, P21/n	Melting point: 435 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 14.1575 (2) Å	Cell parameters from 2708 reflections
b = 6.9399 (1) Å	θ = 1.8–25.0°
c = 15.9750 (2) Å	µ = 0.35 mm−1
β = 101.591 (1)°	T = 296 K
V = 1537.56 (4) Å3	Plate, colourless
Z = 4	0.24 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer	2708 independent reflections
Radiation source: fine-focus sealed tube	2387 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω and φ scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −16→16
Tmin = 0.770, Tmax = 1.000	k = −8→8
14561 measured reflections	l = −18→18

Refinement

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0638P)2 + 0.371P] where P = (Fo2 + 2Fc2)/3
2708 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

Special details

Experimental. IR (KBr): 660 cm-1 (C—S), 1251 cm-1 (C═S), 1036 cm-1 (C—O), 842 cm-1 (C—N), 1279 cm-1 (C—O—C), 1708.6 cm-1 (C═O). GCMS: m/e: 335. 1H NMR (400 MHz, DMSO.D6, δ, p.p.m.): 1.92 (m, 2H, C10), 2.01 (m, 2H, C1), 2.49 (m, 4H, C2, C11), 3.80 (s, 3H, C9), 4.86 (s, 2H, C4), 6.57 (s, 1H, C12), 7.24 (m, 1H, C15), 7.36 (t, 1H, C7), 7.38 (s, 1H, C16). Elemental analysis: C, 57.26; H, 5.07; N, 4.15.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	−0.10475 (3)	0.58858 (7)	0.13224 (3)	0.04867 (17)
S2	−0.13511 (3)	1.01975 (7)	0.13357 (4)	0.05409 (18)
O1	0.15254 (9)	0.74478 (19)	0.41212 (8)	0.0436 (3)
O2	0.01004 (11)	0.7691 (3)	0.44665 (9)	0.0652 (4)
N1	−0.27082 (10)	0.7553 (3)	0.12911 (10)	0.0488 (4)
C1	0.41046 (13)	0.7183 (3)	0.19340 (13)	0.0456 (4)
H1	0.4754	0.7065	0.2185	0.055*
C2	0.38414 (14)	0.7329 (3)	0.10721 (13)	0.0508 (5)
H2	0.4303	0.7288	0.0733	0.061*
C3	0.28694 (14)	0.7539 (3)	0.07027 (13)	0.0499 (5)
H3	0.2688	0.7681	0.0113	0.060*
C4	0.21747 (13)	0.7542 (3)	0.11888 (11)	0.0416 (4)
H4	0.1532	0.7687	0.0921	0.050*
C5	0.24097 (12)	0.7331 (2)	0.20858 (11)	0.0328 (4)
C6	0.34099 (12)	0.7208 (2)	0.24588 (12)	0.0366 (4)
C7	0.17168 (11)	0.7307 (2)	0.26443 (10)	0.0314 (3)
C8	0.20897 (12)	0.7360 (2)	0.35158 (11)	0.0354 (4)
C9	0.30765 (13)	0.7276 (3)	0.38766 (12)	0.0435 (4)
H9	0.3286	0.7302	0.4467	0.052*
C10	0.37191 (12)	0.7158 (3)	0.33586 (12)	0.0426 (4)
H10	0.4373	0.7042	0.3595	0.051*
C11	0.06649 (11)	0.7181 (2)	0.23967 (11)	0.0339 (4)
C12	0.01393 (12)	0.7310 (3)	0.30092 (12)	0.0409 (4)
H12	−0.0529	0.7268	0.2842	0.049*
C13	0.05420 (13)	0.7508 (3)	0.38989 (12)	0.0446 (4)
C14	0.01533 (12)	0.6860 (3)	0.14798 (11)	0.0404 (4)
H14A	0.0544	0.5996	0.1213	0.048*
H14B	0.0123	0.8083	0.1181	0.048*
C15	−0.17873 (12)	0.7969 (3)	0.13185 (11)	0.0397 (4)
C16	−0.31006 (16)	0.5603 (4)	0.12493 (16)	0.0676 (6)
H16A	−0.3781	0.5660	0.1236	0.101*
H16B	−0.2789	0.4888	0.1742	0.101*
H16C	−0.2990	0.4977	0.0742	0.101*
C17	−0.34233 (14)	0.9085 (4)	0.12752 (16)	0.0668 (6)
H17A	−0.4046	0.8523	0.1258	0.100*
H17B	−0.3443	0.9873	0.0778	0.100*
H17C	−0.3249	0.9863	0.1779	0.100*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0357 (3)	0.0472 (3)	0.0603 (3)	−0.00403 (19)	0.0030 (2)	−0.0062 (2)
S2	0.0350 (3)	0.0487 (3)	0.0741 (4)	−0.0002 (2)	0.0003 (2)	0.0049 (2)
O1	0.0400 (7)	0.0563 (7)	0.0364 (6)	0.0031 (5)	0.0123 (5)	0.0014 (5)
O2	0.0541 (9)	0.0994 (12)	0.0492 (8)	0.0075 (8)	0.0273 (7)	0.0011 (8)
N1	0.0305 (8)	0.0658 (10)	0.0500 (9)	−0.0064 (7)	0.0073 (7)	−0.0073 (8)
C1	0.0313 (9)	0.0448 (10)	0.0642 (12)	0.0016 (7)	0.0176 (8)	0.0010 (9)
C2	0.0462 (11)	0.0542 (11)	0.0603 (12)	0.0013 (8)	0.0305 (10)	0.0005 (9)
C3	0.0536 (12)	0.0564 (11)	0.0447 (10)	0.0038 (9)	0.0214 (9)	0.0036 (9)
C4	0.0372 (9)	0.0475 (10)	0.0422 (9)	0.0035 (7)	0.0125 (8)	0.0037 (8)
C5	0.0327 (8)	0.0267 (7)	0.0406 (9)	0.0024 (6)	0.0107 (7)	0.0020 (6)
C6	0.0330 (9)	0.0291 (8)	0.0492 (10)	0.0002 (6)	0.0123 (7)	0.0009 (7)
C7	0.0294 (8)	0.0272 (7)	0.0385 (9)	0.0031 (6)	0.0090 (6)	0.0025 (6)
C8	0.0365 (9)	0.0336 (8)	0.0381 (9)	0.0015 (6)	0.0116 (7)	0.0017 (7)
C9	0.0397 (10)	0.0493 (10)	0.0393 (9)	−0.0007 (8)	0.0026 (7)	0.0006 (8)
C10	0.0291 (8)	0.0437 (10)	0.0525 (10)	0.0000 (7)	0.0025 (7)	0.0017 (8)
C11	0.0311 (8)	0.0318 (8)	0.0393 (9)	0.0039 (6)	0.0080 (7)	0.0027 (6)
C12	0.0295 (8)	0.0464 (10)	0.0476 (10)	0.0032 (7)	0.0097 (7)	0.0041 (8)
C13	0.0395 (10)	0.0511 (10)	0.0463 (10)	0.0044 (8)	0.0163 (8)	0.0042 (8)
C14	0.0305 (8)	0.0471 (10)	0.0439 (9)	0.0031 (7)	0.0082 (7)	−0.0025 (7)
C15	0.0298 (8)	0.0539 (11)	0.0334 (8)	−0.0012 (7)	0.0019 (6)	−0.0023 (7)
C16	0.0446 (12)	0.0797 (16)	0.0781 (15)	−0.0233 (11)	0.0115 (11)	−0.0075 (13)
C17	0.0313 (10)	0.0920 (18)	0.0773 (15)	0.0048 (10)	0.0113 (10)	−0.0135 (13)

Geometric parameters (Å, º)

S1—C15	1.7844 (18)	C6—C10	1.416 (3)
S1—C14	1.7997 (17)	C7—C8	1.387 (2)
S2—C15	1.6637 (18)	C7—C11	1.465 (2)
O1—C13	1.367 (2)	C8—C9	1.401 (2)
O1—C8	1.374 (2)	C9—C10	1.350 (3)
O2—C13	1.207 (2)	C9—H9	0.9300
N1—C15	1.327 (2)	C10—H10	0.9300
N1—C16	1.460 (3)	C11—C12	1.346 (2)
N1—C17	1.465 (3)	C11—C14	1.514 (2)
C1—C2	1.356 (3)	C12—C13	1.428 (3)
C1—C6	1.415 (2)	C12—H12	0.9300
C1—H1	0.9300	C14—H14A	0.9700
C2—C3	1.392 (3)	C14—H14B	0.9700
C2—H2	0.9300	C16—H16A	0.9600
C3—C4	1.370 (2)	C16—H16B	0.9600
C3—H3	0.9300	C16—H16C	0.9600
C4—C5	1.412 (2)	C17—H17A	0.9600
C4—H4	0.9300	C17—H17B	0.9600
C5—C6	1.424 (2)	C17—H17C	0.9600
C5—C7	1.453 (2)
C15—S1—C14	103.50 (8)	C9—C10—H10	119.6
C13—O1—C8	121.63 (14)	C6—C10—H10	119.6
C15—N1—C16	124.41 (17)	C12—C11—C7	118.71 (15)
C15—N1—C17	120.92 (18)	C12—C11—C14	119.09 (15)
C16—N1—C17	114.64 (17)	C7—C11—C14	122.18 (14)
C2—C1—C6	121.25 (17)	C11—C12—C13	124.16 (16)
C2—C1—H1	119.4	C11—C12—H12	117.9
C6—C1—H1	119.4	C13—C12—H12	117.9
C1—C2—C3	119.01 (17)	O2—C13—O1	117.55 (17)
C1—C2—H2	120.5	O2—C13—C12	126.46 (18)
C3—C2—H2	120.5	O1—C13—C12	115.97 (15)
C4—C3—C2	121.41 (19)	C11—C14—S1	116.43 (12)
C4—C3—H3	119.3	C11—C14—H14A	108.2
C2—C3—H3	119.3	S1—C14—H14A	108.2
C3—C4—C5	121.69 (17)	C11—C14—H14B	108.2
C3—C4—H4	119.2	S1—C14—H14B	108.2
C5—C4—H4	119.2	H14A—C14—H14B	107.3
C4—C5—C6	116.26 (15)	N1—C15—S2	124.15 (14)
C4—C5—C7	125.03 (15)	N1—C15—S1	113.33 (14)
C6—C5—C7	118.66 (15)	S2—C15—S1	122.51 (10)
C1—C6—C10	119.42 (16)	N1—C16—H16A	109.5
C1—C6—C5	120.26 (17)	N1—C16—H16B	109.5
C10—C6—C5	120.31 (15)	H16A—C16—H16B	109.5
C8—C7—C5	116.65 (15)	N1—C16—H16C	109.5
C8—C7—C11	115.72 (14)	H16A—C16—H16C	109.5
C5—C7—C11	127.61 (15)	H16B—C16—H16C	109.5
O1—C8—C7	123.37 (15)	N1—C17—H17A	109.5
O1—C8—C9	112.63 (15)	N1—C17—H17B	109.5
C7—C8—C9	123.98 (15)	H17A—C17—H17B	109.5
C10—C9—C8	119.30 (17)	N1—C17—H17C	109.5
C10—C9—H9	120.4	H17A—C17—H17C	109.5
C8—C9—H9	120.4	H17B—C17—H17C	109.5
C9—C10—C6	120.78 (16)
C6—C1—C2—C3	1.1 (3)	C8—C9—C10—C6	3.0 (3)
C1—C2—C3—C4	−2.0 (3)	C1—C6—C10—C9	176.69 (17)
C2—C3—C4—C5	−0.1 (3)	C5—C6—C10—C9	−1.8 (3)
C3—C4—C5—C6	2.9 (3)	C8—C7—C11—C12	6.2 (2)
C3—C4—C5—C7	−179.57 (17)	C5—C7—C11—C12	−175.55 (15)
C2—C1—C6—C10	−176.61 (17)	C8—C7—C11—C14	−172.20 (15)
C2—C1—C6—C5	1.9 (3)	C5—C7—C11—C14	6.1 (2)
C4—C5—C6—C1	−3.8 (2)	C7—C11—C12—C13	−1.9 (3)
C7—C5—C6—C1	178.55 (15)	C14—C11—C12—C13	176.53 (16)
C4—C5—C6—C10	174.68 (15)	C8—O1—C13—O2	−176.03 (17)
C7—C5—C6—C10	−3.0 (2)	C8—O1—C13—C12	5.1 (2)
C4—C5—C7—C8	−171.14 (16)	C11—C12—C13—O2	177.5 (2)
C6—C5—C7—C8	6.3 (2)	C11—C12—C13—O1	−3.8 (3)
C4—C5—C7—C11	10.6 (3)	C12—C11—C14—S1	−20.2 (2)
C6—C5—C7—C11	−171.94 (15)	C7—C11—C14—S1	158.21 (12)
C13—O1—C8—C7	−0.7 (2)	C15—S1—C14—C11	86.48 (14)
C13—O1—C8—C9	−178.99 (16)	C16—N1—C15—S2	178.01 (16)
C5—C7—C8—O1	176.45 (14)	C17—N1—C15—S2	−0.1 (3)
C11—C7—C8—O1	−5.1 (2)	C16—N1—C15—S1	−1.3 (2)
C5—C7—C8—C9	−5.4 (2)	C17—N1—C15—S1	−179.39 (14)
C11—C7—C8—C9	173.06 (15)	C14—S1—C15—N1	−173.89 (13)
O1—C8—C9—C10	179.10 (16)	C14—S1—C15—S2	6.82 (14)
C7—C8—C9—C10	0.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2i	0.93	2.51	3.405 (3)	162

Symmetry code: (i) x+1/2, −y+3/2, z−1/2.