Aceton­yl morpholine 4 carbodi­thio­ate

organic papers

o2426

8H13NO2S2 doi:10.1107/S1600536805020891 Acta Cryst.(2005). E61, o2426–o2427

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

Acetonyl morpholine-4-carbodithioate

Jun Wan, Chun-Li Li, Xue-Mei Li and Shu-Sheng Zhang*

College of Chemistry and Molecular

Engineering, Qingdao University of Science and Technology, 266042 Qingdao, Shandong, People’s Republic of China

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.004 A˚

Rfactor = 0.034

wRfactor = 0.099

Data-to-parameter ratio = 17.4

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography

Printed in Great Britain – all rights reserved

In the title molecule, C8H13NO2S2, the morpholine ring adopts

a chair conformation. In the crystal structure, a short intermolecular O S interaction [3.214 (2) A˚ ] links the mol-ecules into spiral chains along thebaxis.

Comment

Morpholine derivatives, as an important type of fungicides, have attracted much interest because of their inward absor-bent and broad-spectrum activities (Badioli et al., 2002). Dialkyl-substituted dithiocarbamate salts have shown inter-esting biological effects as broad-range fungicides. In order to search for new morpholine compounds with high bioactivity, the title compound, (I), was synthesized. We present here its crystal structure.

The bond lengths and angles in (I) (Table 1) are within normal ranges (Allenet al., 1987) and comparable with those in a related compound (Ko¨ysalet al., 2004). The morpholine ring adopts a chair conformation (Fig. 1), with atoms O1 and N1 deviating by 0.66 (2) and 0.57 (1) A˚ , respectively, from the mean plane through atoms C1–C4. There are three intramolecular C—H S interactions (Table 2), each forming a five-membered ring. In the crystal structure, short inter-molecular contacts O2 S1i[3.214 (2) A˚ ; symmetry code: (i)

1 x, 1

2+y, 1

2z] link the molecules into spiral chains

along thebaxis (Fig. 2).

Experimental

1-Bromoacetone was prepared by the reaction of acetone (3.7 ml, 0.05 mol) and bromine (8.0 g, 2.6 ml) in anhydrous diethyl ether according to Xu et al. (2002). (4-Morpholinylcarbothioyl)-sulfanylamine was prepared by reacting morpholine (3.9 ml, 0.05 mol) with carbon disulfide (3.0 ml, 0.05 mol) in ammonia (25– 28%, 10 ml). The title compound was synthesized by reacting 1-bromoacetone and (4-morpholinylcarbothioyl)sulfanylamine in acetone at room temperature for 2 h. The solution was filtered and purified by flash chromatography (silica gel, petroleum ether–ethyl acetate 6:1 (v/v). Single crystals suitable for X-ray diffraction study were obtained by slow evaporation of an ethyl acetate–petroleum ether (1:1 (v/v) solution over a period of two weeks.

Crystal data

C8H13NO2S2

Mr= 219.31 Monoclinic,P21=c

a= 15.043 (2) A˚ b= 4.9119 (7) A˚ c= 17.1097 (17) A˚

= 123.848 (8) V= 1050.0 (2) A˚3 Z= 4

Dx= 1.387 Mg m3 MoKradiation Cell parameters from 2917

reflections

= 2.9–26.0

= 0.48 mm1

T= 293 (2) K Block, colourless 0.500.220.07 mm

Data collection

Siemens SMART 1000 CCD area-detector diffractometer

!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin= 0.797,Tmax= 0.968

5540 measured reflections

2048 independent reflections 1794 reflections withI> 2(I) Rint= 0.013

max= 26.1

h=18!17 k=5!6 l=11!21

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.034 wR(F2_{) = 0.099}

S= 1.07 2048 reflections 118 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0575P)2

+ 0.1984P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.20 e A˚

3

min=0.19 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

S1—C5 1.7754 (16)

S1—C6 1.7831 (18)

S2—C5 1.6604 (16)

O1—C2 1.405 (3)

O1—C3 1.421 (3)

N1—C5 1.330 (2)

N1—C4 1.471 (2)

N1—C1 1.473 (2)

C5—S1—C6 102.24 (8)

N1—C5—S2 124.69 (12)

N1—C5—S1 113.31 (12)

S2—C5—S1 121.99 (10)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

C1—H1A S1 0.97 2.37 2.901 (3) 114

C4—H4B S2 0.97 2.57 3.048 (2) 111

C6—H6A S2 0.97 2.69 3.057 (2) 103

All H atoms were located in difference Fourier maps and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 A˚ and withUiso(H) = 1.2Ueq(C).

Data collection:SMART(Siemens, 1996); cell refinement:SAINT

(Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure:SHELXTL; molecular graphics:SHELXTL; software used

to prepare material for publication:SHELXTL,PARST(Nardelli, 1995) andPLATON(Spek, 2003).

This project was supported by the Program for New Century Excellent Talents in University (No. NCET-04–0649), and the Project of Educational Administration of Shandong Province (No. J04B12).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987).J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Badioli, M., Ballini, R., Bartolacci, M., Bosica, G., Torregiani, E. & Marcantoni, E. (2002).J. Org. Chem.67, 8938–8942.

Ko¨ysal, Y., Isik, S., Septioglu, E. & Calis, U. (2004).Acta Cryst.C60, o757– o758.

Nardelli, M. (1995).J. Appl. Cryst.28, 659.

Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997).SHELXTL. Version 5.1. Bruker AXS Inc., Madison,

Wisconsin, USA.

Siemens (1996).SMARTandSAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

Xu, L. Z., Jiao, K., Zhang, S. S. & Kuang, S. P. (2002).Bull. Kor. Chem. Soc.23, 1699–1701.

Figure 2

The crystal packing, viewed approximately down thecaxis, showing the short intermolecular O S interactions (dashed lines).

Figure 1

supporting information

sup-1 Acta Cryst. (2005). E61, o2426–o2427

supporting information

Acta Cryst. (2005). E61, o2426–o2427 [https://doi.org/10.1107/S1600536805020891]

Acetonyl morpholine-4-carbodithioate

Jun Wan, Chun-Li Li, Xue-Mei Li and Shu-Sheng Zhang

Acetonyl morpholine-4-carbodithioate

Crystal data

C8H13NO2S2

Mr = 219.31

Monoclinic, P21/c

a = 15.043 (2) Å b = 4.9119 (7) Å c = 17.1097 (17) Å β = 123.848 (8)° V = 1050.0 (2) Å3

Z = 4

F(000) = 464 Dx = 1.387 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2917 reflections θ = 2.9–26.0°

µ = 0.48 mm−1

T = 293 K Block, colourless 0.50 × 0.22 × 0.07 mm

Data collection

Siemens SMART 1000 CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 8.33 pixels mm-1

ω scans

Absorption correction: empirical (using intensity measurements)

(SADABS; Sheldrick, 1996)

Tmin = 0.797, Tmax = 0.968

5540 measured reflections 2048 independent reflections 1794 reflections with I > 2σ(I) Rint = 0.013

θmax = 26.1°, θmin = 1.6°

h = −18→17 k = −5→6 l = −11→21

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.034}

wR(F2_{) = 0.099}

S = 1.07 2048 reflections 118 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0575P)2 + 0.1984P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.20 e Å−3

Δρmin = −0.19 e Å−3

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

S1 0.34990 (3) −0.40882 (10) −0.28135 (3) 0.05330 (17)

S2 0.16710 (4) −0.56402 (10) −0.47601 (3) 0.05674 (17)

O1 0.09755 (14) −0.9550 (4) −0.22966 (12) 0.0856 (5)

N1 0.19435 (11) −0.7322 (3) −0.31665 (9) 0.0516 (4)

C7 0.40725 (14) −0.3467 (4) −0.41015 (13) 0.0521 (4)

O2 0.45425 (12) −0.5599 (3) −0.38385 (11) 0.0721 (4)

C1 0.25426 (15) −0.7714 (5) −0.21403 (12) 0.0618 (5)

H1A 0.3080 −0.6300 −0.1825 0.074*

H1B 0.2905 −0.9460 −0.1974 0.074*

C2 0.17967 (17) −0.7611 (5) −0.18258 (14) 0.0679 (5)

H2A 0.2195 −0.7944 −0.1154 0.081*

H2B 0.1484 −0.5807 −0.1944 0.081*

C3 0.03533 (17) −0.8969 (5) −0.32760 (16) 0.0739 (6)

H3A 0.0043 −0.7168 −0.3376 0.089*

H3B −0.0229 −1.0270 −0.3596 0.089*

C4 0.09967 (16) −0.9088 (4) −0.36932 (14) 0.0608 (5)

H4A 0.1222 −1.0948 −0.3679 0.073*

H4B 0.0560 −0.8505 −0.4345 0.073*

C5 0.22899 (12) −0.5862 (3) −0.36005 (11) 0.0429 (4)

C6 0.36472 (14) −0.2036 (4) −0.35938 (13) 0.0529 (4)

H6A 0.2955 −0.1261 −0.4061 0.063*

H6B 0.4124 −0.0539 −0.3237 0.063*

C8 0.3897 (2) −0.1986 (5) −0.49329 (18) 0.0850 (7)

H8A 0.4188 −0.3027 −0.5215 0.128*

H8B 0.4247 −0.0247 −0.4738 0.128*

H8C 0.3144 −0.1726 −0.5383 0.128*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

S1 0.0451 (3) 0.0659 (3) 0.0473 (3) −0.00952 (18) 0.0247 (2) −0.00917 (19)

S2 0.0552 (3) 0.0718 (3) 0.0395 (3) −0.0034 (2) 0.0241 (2) −0.00283 (19)

O1 0.0931 (11) 0.1046 (13) 0.0788 (10) −0.0303 (9) 0.0600 (9) 0.0004 (9)

N1 0.0474 (8) 0.0688 (9) 0.0431 (7) −0.0112 (7) 0.0280 (6) −0.0096 (7)

C7 0.0504 (9) 0.0485 (9) 0.0594 (10) −0.0033 (7) 0.0320 (8) −0.0009 (8)

O2 0.0791 (10) 0.0654 (9) 0.0858 (10) 0.0227 (7) 0.0546 (9) 0.0123 (7)

C1 0.0593 (11) 0.0831 (13) 0.0460 (9) −0.0043 (10) 0.0312 (9) −0.0021 (9)

C2 0.0812 (13) 0.0818 (14) 0.0574 (11) −0.0074 (11) 0.0491 (10) −0.0008 (10)

C3 0.0652 (13) 0.0954 (17) 0.0723 (14) −0.0220 (11) 0.0451 (11) −0.0121 (11)

supporting information

sup-3 Acta Cryst. (2005). E61, o2426–o2427

C5 0.0401 (8) 0.0479 (9) 0.0425 (8) 0.0015 (6) 0.0241 (7) −0.0075 (6)

C6 0.0522 (9) 0.0451 (9) 0.0635 (11) −0.0039 (7) 0.0337 (8) −0.0045 (8)

C8 0.121 (2) 0.0705 (14) 0.0863 (16) 0.0011 (14) 0.0721 (16) 0.0111 (12)

Geometric parameters (Å, º)

S1—C5 1.7754 (16) C1—H1B 0.9700

S1—C6 1.7831 (18) C2—H2A 0.9700

S2—C5 1.6604 (16) C2—H2B 0.9700

O1—C2 1.405 (3) C3—C4 1.490 (3)

O1—C3 1.421 (3) C3—H3A 0.9700

N1—C5 1.330 (2) C3—H3B 0.9700

N1—C4 1.471 (2) C4—H4A 0.9700

N1—C1 1.473 (2) C4—H4B 0.9700

C7—O2 1.202 (2) C6—H6A 0.9700

C7—C8 1.485 (3) C6—H6B 0.9700

C7—C6 1.509 (2) C8—H8A 0.9600

C1—C2 1.491 (2) C8—H8B 0.9600

C1—H1A 0.9700 C8—H8C 0.9600

C5—S1—C6 102.24 (8) C4—C3—H3B 109.1

C2—O1—C3 109.37 (16) H3A—C3—H3B 107.9

C5—N1—C4 121.52 (14) N1—C4—C3 110.45 (16)

C5—N1—C1 124.48 (14) N1—C4—H4A 109.6

C4—N1—C1 113.22 (15) C3—C4—H4A 109.6

O2—C7—C8 122.63 (19) N1—C4—H4B 109.6

O2—C7—C6 122.67 (17) C3—C4—H4B 109.6

C8—C7—C6 114.66 (17) H4A—C4—H4B 108.1

N1—C1—C2 110.00 (16) N1—C5—S2 124.69 (12)

N1—C1—H1A 109.7 N1—C5—S1 113.31 (12)

C2—C1—H1A 109.7 S2—C5—S1 121.99 (10)

N1—C1—H1B 109.7 C7—C6—S1 115.96 (13)

C2—C1—H1B 109.7 C7—C6—H6A 108.3

H1A—C1—H1B 108.2 S1—C6—H6A 108.3

O1—C2—C1 111.60 (17) C7—C6—H6B 108.3

O1—C2—H2A 109.3 S1—C6—H6B 108.3

C1—C2—H2A 109.3 H6A—C6—H6B 107.4

O1—C2—H2B 109.3 C7—C8—H8A 109.5

C1—C2—H2B 109.3 C7—C8—H8B 109.5

H2A—C2—H2B 108.0 H8A—C8—H8B 109.5

O1—C3—C4 112.35 (18) C7—C8—H8C 109.5

O1—C3—H3A 109.1 H8A—C8—H8C 109.5

C4—C3—H3A 109.1 H8B—C8—H8C 109.5

O1—C3—H3B 109.1

C5—N1—C1—C2 140.45 (18) C1—N1—C5—S2 174.18 (14)

C4—N1—C1—C2 −49.6 (2) C4—N1—C5—S1 −175.64 (13)

N1—C1—C2—O1 56.7 (2) C6—S1—C5—N1 −172.76 (12)

C2—O1—C3—C4 61.0 (3) C6—S1—C5—S2 6.65 (12)

C5—N1—C4—C3 −141.50 (19) O2—C7—C6—S1 −18.8 (2)

C1—N1—C4—C3 48.2 (2) C8—C7—C6—S1 163.18 (16)

O1—C3—C4—N1 −53.6 (3) C5—S1—C6—C7 −78.56 (14)

C4—N1—C5—S2 5.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C1—H1A···S1 0.97 2.37 2.901 (3) 114

C4—H4B···S2 0.97 2.57 3.048 (2) 111