1,2-Dimorpholinoethane-1,2-dithione

Yu, Y.-P.; Lin, Y.-Y.; Liu, B.-X.

doi:10.1107/S1600536809001780

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o511

doi:10.1107/S1600536809001780

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1,2-Dimorpholinoethane-1,2-dithione

Yan-Ping Yu,^a Yuan-Yuan Lin ^a and Bing-Xin Liu ^a ^*

^aDepartment of Chemistry, Shanghai University, People's Republic of China
^*Correspondence e-mail: r5744011@yahoo.com.cn

(Received 6 October 2008; accepted 14 January 2009; online 11 February 2009)

The title compound, C₁₀H₁₆N₂O₂S₂, was prepared by a reaction of 4-tert-butylbenzene, morpholine and sulfur. In the crystal structure, both morpholine rings display the typical chair conformation. Weak C—H⋯O hydrogen bonding is present in the crystal structure.

Related literature

For general background, see: Carmack (1989 ). For a related structure, see: Rozentsveig et al. (2005 ).

Experimental

Crystal data

C₁₀H₁₆N₂O₂S₂
M_r = 260.37
Monoclinic, C 2/c
a = 34.661 (7) Å
b = 6.5155 (12) Å
c = 10.6632 (19) Å
β = 93.633 (2)°
V = 2403.3 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 295 (2) K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.905, T_max = 0.940
6026 measured reflections
2118 independent reflections
1673 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.086
S = 1.05
2118 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯O1ⁱ	0.97	2.51	3.400 (3)	153
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809001780/xu2457sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001780/xu2457Isup2.hkl

checkCIF report

Comment top

Willgerodt-Kindler reaction is an important synthesize reaction of medicament, but the reaction mechanism is not completely clear (Carmack, 1989). To investigate the reaction mechanism of Willgerodt-Kindler reaction, we performed the reaction of morpholine with 4-tert-butylphenyl and sulfur and obtained single crystals of the title compound. Herein we present its X-ray structure.

The molecular structure of the title compound is shown in Fig. 1. Within the molecule structure, two C═S bond distances are 1.656 (2) Å and 1.666 (2) Å, respectively. The two planes containing the C—S bonds, C1/C4/N1/C5/S1 and C7/C10/N2/C6/S2, are nearly perpendicular to each other with a dihedral angle of 89.94 (7)°. Both morpholino rings display the typical chair conformation, which agrees with that found in the dimorpholine derivative, 4-chloro-N-(2-(4-methylphenyl)-1,2-dimorpholinoethylidene)benzenesulfonamide (Rozentsveig et al., 2005). The adjacent molecules are linked together via C—H···O weak hydrogen bonding (Table 1).

Related literature top

For general background, see: Carmack (1989). For a related structure, see: Rozentsveig et al. (2005).

Experimental top

The title compound was prepared by a reaction of 4'-tert-butylacetophenone (17.72 g, 0.1 mol), morpholine (33 ml, 0.375 mol) and sulfur (5.29 g, 0.165 mol) at 397–405 K until the reaction mixture changed color to puce. Add methanol (100 ml) and active carbon (1 g) into the reaction mixture after the reaction undergoing 10 h. After the reaction mixture cooling to room temperature, the filemot solid product was separated from the reaction mixture. The filemot solid product and was mixed with an ethanol-water solution (1:3) and an aqueous solution (20 ml) of NaOH (0.05 g 1.14 mmol). The mixture was refluxed for 4 h at 357 K and the kelly depositions were obtained from the cooling reaction mixture. The single crystals of the title compound were obtained by recrystallization of the solid product from an ethanol solution after 2 d.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids.

1,2-Dimorpholinoethane-1,2-dithione top

Crystal data top

C₁₀H₁₆N₂O₂S₂	F(000) = 1104
M_r = 260.37	D_x = 1.439 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2010 reflections
a = 34.661 (7) Å	θ = 2.0–25.0°
b = 6.5155 (12) Å	µ = 0.43 mm⁻¹
c = 10.6632 (19) Å	T = 295 K
β = 93.633 (2)°	Prism, colorless
V = 2403.3 (8) Å³	0.25 × 0.20 × 0.15 mm
Z = 8

Data collection top

Bruker APEX CCD diffractometer	2118 independent reflections
Radiation source: fine-focus sealed tube	1673 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −39→40
T_min = 0.905, T_max = 0.940	k = −7→7
6026 measured reflections	l = −12→7

Refinement top

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) = 0.086	w = 1/[σ²(F_o²) + (0.0357P)² + 1.3632P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2118 reflections	Δρ_max = 0.19 e Å⁻³
146 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0028 (3)

Crystal data top

C₁₀H₁₆N₂O₂S₂	V = 2403.3 (8) Å³
M_r = 260.37	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 34.661 (7) Å	µ = 0.43 mm⁻¹
b = 6.5155 (12) Å	T = 295 K
c = 10.6632 (19) Å	0.25 × 0.20 × 0.15 mm
β = 93.633 (2)°

Data collection top

Bruker APEX CCD diffractometer	2118 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1673 reflections with I > 2σ(I)
T_min = 0.905, T_max = 0.940	R_int = 0.029
6026 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.05	Δρ_max = 0.19 e Å⁻³
2118 reflections	Δρ_min = −0.20 e Å⁻³
146 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
S1	0.372884 (17)	−0.19547 (8)	0.11699 (5)	0.0400 (2)
S2	0.380220 (17)	0.28649 (9)	0.28638 (5)	0.04075 (19)
N1	0.32643 (5)	0.1044 (3)	0.03467 (16)	0.0338 (4)
N2	0.41166 (5)	0.2706 (3)	0.06457 (16)	0.0322 (4)
O1	0.27344 (4)	0.2067 (3)	−0.16300 (16)	0.0515 (5)
O2	0.48123 (4)	0.2411 (3)	−0.04519 (17)	0.0557 (5)
C1	0.29717 (6)	−0.0402 (4)	−0.0084 (2)	0.0458 (6)
H1A	0.2748	−0.0269	0.0412	0.055*
H1B	0.3070	−0.1790	0.0014	0.055*
C2	0.28575 (7)	0.0009 (4)	−0.1446 (2)	0.0504 (6)
H2A	0.3076	−0.0258	−0.1947	0.060*
H2B	0.2650	−0.0913	−0.1727	0.060*
C3	0.30297 (7)	0.3439 (4)	−0.1261 (2)	0.0489 (6)
H3A	0.2940	0.4833	−0.1412	0.059*
H3B	0.3249	0.3208	−0.1765	0.059*
C4	0.31559 (6)	0.3191 (3)	0.0111 (2)	0.0400 (6)
H4A	0.3375	0.4079	0.0327	0.048*
H4B	0.2947	0.3573	0.0626	0.048*
C5	0.35897 (6)	0.0447 (3)	0.09058 (18)	0.0294 (5)
C6	0.38568 (6)	0.2090 (3)	0.13964 (18)	0.0288 (5)
C7	0.41350 (6)	0.2047 (3)	−0.0666 (2)	0.0356 (5)
H7A	0.4101	0.3225	−0.1218	0.043*
H7B	0.3928	0.1081	−0.0878	0.043*
C8	0.45103 (6)	0.1074 (4)	−0.0844 (2)	0.0490 (6)
H8A	0.4532	−0.0187	−0.0361	0.059*
H8B	0.4529	0.0733	−0.1724	0.059*
C9	0.47931 (6)	0.2926 (4)	0.0832 (2)	0.0508 (6)
H9A	0.5013	0.3783	0.1093	0.061*
H9B	0.4809	0.1682	0.1333	0.061*
C10	0.44318 (6)	0.4028 (4)	0.1069 (2)	0.0433 (6)
H10A	0.4421	0.4320	0.1958	0.052*
H10B	0.4418	0.5315	0.0611	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0510 (4)	0.0286 (3)	0.0395 (4)	0.0032 (3)	−0.0054 (3)	0.0015 (2)
S2	0.0501 (4)	0.0399 (3)	0.0323 (3)	−0.0051 (3)	0.0034 (3)	−0.0076 (2)
N1	0.0288 (9)	0.0299 (9)	0.0418 (11)	−0.0012 (8)	−0.0053 (8)	0.0005 (8)
N2	0.0271 (9)	0.0358 (10)	0.0336 (10)	−0.0022 (8)	0.0007 (7)	−0.0031 (8)
O1	0.0382 (9)	0.0582 (11)	0.0560 (11)	0.0050 (8)	−0.0147 (7)	0.0016 (8)
O2	0.0339 (9)	0.0722 (12)	0.0620 (12)	−0.0023 (8)	0.0117 (8)	−0.0043 (9)
C1	0.0345 (12)	0.0426 (14)	0.0587 (16)	−0.0099 (11)	−0.0092 (11)	0.0003 (11)
C2	0.0424 (14)	0.0558 (16)	0.0512 (16)	−0.0012 (12)	−0.0115 (11)	−0.0101 (12)
C3	0.0402 (13)	0.0461 (15)	0.0594 (16)	0.0046 (12)	−0.0054 (11)	0.0089 (12)
C4	0.0301 (11)	0.0351 (12)	0.0539 (15)	0.0058 (10)	−0.0048 (10)	−0.0021 (10)
C5	0.0327 (11)	0.0323 (11)	0.0234 (11)	0.0004 (9)	0.0030 (8)	−0.0003 (9)
C6	0.0273 (10)	0.0266 (11)	0.0320 (12)	0.0036 (9)	−0.0032 (9)	0.0025 (9)
C7	0.0347 (12)	0.0405 (13)	0.0316 (12)	0.0002 (10)	0.0013 (9)	0.0012 (10)
C8	0.0437 (14)	0.0554 (16)	0.0486 (15)	0.0028 (12)	0.0090 (11)	−0.0080 (12)
C9	0.0314 (13)	0.0636 (17)	0.0571 (17)	−0.0067 (12)	−0.0003 (11)	0.0028 (13)
C10	0.0344 (12)	0.0436 (14)	0.0517 (15)	−0.0106 (11)	0.0020 (10)	−0.0075 (11)

Geometric parameters (Å, º) top

S1—C5	1.656 (2)	C3—C4	1.509 (3)
S2—C6	1.666 (2)	C3—H3A	0.9700
N1—C5	1.301 (2)	C3—H3B	0.9700
N1—C1	1.438 (3)	C4—H4A	0.9700
N1—C4	1.466 (3)	C4—H4B	0.9700
N2—C6	1.305 (3)	C5—C6	1.488 (3)
N2—C10	1.441 (2)	C7—C8	1.470 (3)
N2—C7	1.468 (3)	C7—H7A	0.9700
O1—C3	1.397 (3)	C7—H7B	0.9700
O1—C2	1.417 (3)	C8—H8A	0.9700
O2—C8	1.405 (3)	C8—H8B	0.9700
O2—C9	1.415 (3)	C9—C10	1.479 (3)
C1—C2	1.505 (3)	C9—H9A	0.9700
C1—H1A	0.9700	C9—H9B	0.9700
C1—H1B	0.9700	C10—H10A	0.9700
C2—H2A	0.9700	C10—H10B	0.9700
C2—H2B	0.9700

C5—N1—C1	121.59 (18)	H4A—C4—H4B	108.3
C5—N1—C4	124.67 (17)	N1—C5—C6	116.62 (18)
C1—N1—C4	113.73 (16)	N1—C5—S1	126.50 (16)
C6—N2—C10	122.03 (18)	C6—C5—S1	116.84 (14)
C6—N2—C7	124.58 (17)	N2—C6—C5	116.33 (18)
C10—N2—C7	113.29 (17)	N2—C6—S2	127.33 (16)
C3—O1—C2	110.98 (16)	C5—C6—S2	116.28 (15)
C8—O2—C9	110.79 (18)	N2—C7—C8	109.97 (17)
N1—C1—C2	109.19 (19)	N2—C7—H7A	109.7
N1—C1—H1A	109.8	C8—C7—H7A	109.7
C2—C1—H1A	109.8	N2—C7—H7B	109.7
N1—C1—H1B	109.8	C8—C7—H7B	109.7
C2—C1—H1B	109.8	H7A—C7—H7B	108.2
H1A—C1—H1B	108.3	O2—C8—C7	110.04 (19)
O1—C2—C1	111.12 (19)	O2—C8—H8A	109.7
O1—C2—H2A	109.4	C7—C8—H8A	109.7
C1—C2—H2A	109.4	O2—C8—H8B	109.7
O1—C2—H2B	109.4	C7—C8—H8B	109.7
C1—C2—H2B	109.4	H8A—C8—H8B	108.2
H2A—C2—H2B	108.0	O2—C9—C10	111.87 (19)
O1—C3—C4	111.5 (2)	O2—C9—H9A	109.2
O1—C3—H3A	109.3	C10—C9—H9A	109.2
C4—C3—H3A	109.3	O2—C9—H9B	109.2
O1—C3—H3B	109.3	C10—C9—H9B	109.2
C4—C3—H3B	109.3	H9A—C9—H9B	107.9
H3A—C3—H3B	108.0	N2—C10—C9	106.86 (19)
N1—C4—C3	108.89 (18)	N2—C10—H10A	110.4
N1—C4—H4A	109.9	C9—C10—H10A	110.4
C3—C4—H4A	109.9	N2—C10—H10B	110.4
N1—C4—H4B	109.9	C9—C10—H10B	110.4
C3—C4—H4B	109.9	H10A—C10—H10B	108.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O1ⁱ	0.97	2.51	3.400 (3)	153

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₆N₂O₂S₂
M_r	260.37
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	34.661 (7), 6.5155 (12), 10.6632 (19)
β (°)	93.633 (2)
V (Å³)	2403.3 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.43
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.905, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	6026, 2118, 1673
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.086, 1.05
No. of reflections	2118
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.20

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O1ⁱ	0.97	2.51	3.400 (3)	153

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

Acknowledgements

The project was supported by the Educational Development Foundation of the Shanghai Educational Committee, China (AB0448).

References

Bruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Winsonsin, USA. Google Scholar
Carmack, M. (1989). J. Heterocycl. Chem. 26, 1319–1323. CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Rozentsveig, I. B., Levkovskaya, G. G., Rozentsveig, G. N., Mirskova, A. N., Krivdin, L. B., Larina, L. I. & Albanov, A. I. (2005). Tetrahedron Lett. 46, 8889–8893. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar