supplementary materials
1,2-Dimorpholinoethane-1,2-dithione
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.
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.
H atoms were placed in calculated positions with C—H = 0.97 Å and
included in the final cycles of refinement in riding mode with
Uiso(H) = 1.2Ueq(C).
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).
1,2-Dimorpholinoethane-1,2-dithione
top
Crystal data top
| C10H16N2O2S2 | F(000) = 1104 |
| Mr = 260.37 | Dx = 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 | Rint = 0.029 |
| φ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −39→40 |
| Tmin = 0.905, Tmax = 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(Fo2) + (0.0357P)2 + 1.3632P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.05 | (Δ/σ)max < 0.001 |
| 2118 reflections | Δρmax = 0.19 e Å−3 |
| 146 parameters | Δρmin = −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 |
| Mr = 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) |
| Tmin = 0.905, Tmax = 0.940 | Rint = 0.029 |
| 6026 measured reflections | θmax = 25.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
| wR(F2) = 0.086 | Δρmax = 0.19 e Å−3 |
| S = 1.05 | Δρmin = −0.20 e Å−3 |
| 2118 reflections | Absolute structure: ? |
| 146 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | Uiso*/Ueq | |
| 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, °) 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, °) 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 codes: (i) −x+1/2, y−1/2, −z−1/2. |
Table 1
Hydrogen-bond geometry (Å, °) 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 codes: (i) −x+1/2, y−1/2, −z−1/2. |
The project was supported by the Educational Development Foundation of Shanghai
Educational Committee, China (AB0448).
Bruker (2004). SMART and SAINT. Bruker AXS Inc., Madison, Winsonsin, USA.
Carmack, M. (1989). J. Heterocycl. Chem. 26, 1319–1323.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
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.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./xu2457fig1thm.gif)
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).