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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2671.
Published online 2010 September 30. doi:  10.1107/S160053681003833X
PMCID: PMC2983331

[(Methyl­carbamothio­yl)disulfan­yl]methyl N-methyl­carbamodithio­ate

Abstract

The title compound, C5H10N2S5, was unintentionally obtained as the product of an attempted synthesis of a methyl­carbamodithioic acid using methyl­amine and carbon disulfide. In the mol­ecule, two dithio­carbamate groups are bridged by a –CH2S– unit. The C—S—S—C torsion angle is −90.13 (11)°. The crystal structure is stabilized by N—H(...)S inter­actions between neighbouring mol­ecules. An intra­molecular N—H(...)S hydrogen bond also occurs.

Related literature

For dithio­carbamate ligands, see: Cox et al. (1999 [triangle]); Liu & Bao (2007 [triangle]); Nair et al. (2002 [triangle]).

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Object name is e-66-o2671-scheme1.jpg

Experimental

Crystal data

  • C5H10N2S5
  • M r = 258.45
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2671-efi1.jpg
  • a = 7.188 (1) Å
  • b = 7.884 (2) Å
  • c = 10.219 (2) Å
  • α = 101.23 (3)°
  • β = 96.85 (3)°
  • γ = 102.74 (3)°
  • V = 546.0 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.01 mm−1
  • T = 293 K
  • 0.30 × 0.11 × 0.10 mm

Data collection

  • Stoe IPDS diffractometer
  • 4080 measured reflections
  • 2077 independent reflections
  • 1924 reflections with I > 2σ(I)
  • R int = 0.101

Refinement

  • R[F 2 > 2σ(F 2)] = 0.040
  • wR(F 2) = 0.103
  • S = 1.15
  • 2077 reflections
  • 111 parameters
  • H-atom parameters constrained
  • Δρmax = 0.53 e Å−3
  • Δρmin = −0.37 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-RED32 (Stoe & Cie, 2002 [triangle]); data reduction: X-RED32; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2007 [triangle]); software used to prepare material for publication: enCIFer (Allen et al., 2004 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681003833X/om2358sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681003833X/om2358Isup2.hkl

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

Acknowledgments

The authors thank the Higher Education Commission of Pakistan (HEC) for financial support.

supplementary crystallographic information

Comment

Sulfur-containing organic compounds like dithiocarbamates and xanthates have been used as exceleant metal complexing agents. They have applications as fungicides, pesticides, chelating agents for removal of heavy metal ions from toxic waste, precursors for metal-organic chemical vapour deposition (MOCVD) and synthesis of semi-conductor nanoparticles (Cox & Tiekink, et al., 1999; Nair et al., 2002.) Dithiocarbamates have also been used as protection groups in peptide synthesis, as linkers in solid phase organic synthesis and recently in the synthesis of ionic ligands (Liu et al., 2007.) In the title compound (Fig. 1), the disulfide portion is substatially twisted, with C–S–S–C torsion angle of -90.13 (11)°. The molecular packing also features intra- and intermolecular N—H···S interactions (Table 1).

Experimental

Distilled methylamine (3.00 g, 96.8 mmol) was added in purified methanol (30 ml) in a two neck flask (250 ml) and stirred for ten minutes at 273 K. Carbon disulfide 7.4 ml (117 mmol) was added drop by drop into the two neck flask containing methylamine and a colorless precipitate was formed at once. The stirring was continued for three hours to complete the reaction. The solvent was removed by vacuum distillation. The solid product was washed several times with methanol. The colorless product was purified by recrystallization from 1,1-dichloromethane/pet ether (8:2) V/V), to give fine crystals of the title compound with an overall yield of 85%.

Refinement

All hydrogen atoms were initially located in a difference Fourier map. H atoms on C and N were refined with a riding model, C-H = 0.96 Å with Uiso(H) = 1.5Ueq(C) for methyl groups, C-H = 0.97 Å with Uiso(H) = 1.2 Ueq(C) for methylene groups, and N-H = 0.86 Å with Uiso(H) = 1.2 Ueq(C).

Figures

Fig. 1.
The molecular structure with atom labels and 50% probability displacement ellipsoids for non-H atoms.

Crystal data

C5H10N2S5V = 546.0 (2) Å3
Mr = 258.45Z = 2
Triclinic, P1F(000) = 268
a = 7.188 (1) ÅDx = 1.572 Mg m3
b = 7.884 (2) ÅMo Kα radiation, λ = 0.71073 Å
c = 10.219 (2) ŵ = 1.01 mm1
α = 101.23 (3)°T = 293 K
β = 96.85 (3)°Needle, yellow
γ = 102.74 (3)°0.30 × 0.11 × 0.10 mm

Data collection

Stoe IPDS diffractometer1924 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.101
graphiteθmax = 26.4°, θmin = 4.1°
ω scansh = −8→8
4080 measured reflectionsk = −9→9
2077 independent reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-atom parameters constrained
S = 1.15w = 1/[σ2(Fo2) + (0.0496P)2 + 0.0335P] where P = (Fo2 + 2Fc2)/3
2077 reflections(Δ/σ)max = 0.001
111 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = −0.37 e Å3

Special details

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)

xyzUiso*/Ueq
S10.24777 (9)0.73176 (9)0.11879 (5)0.04736 (19)
S20.39011 (7)0.69015 (8)0.38202 (5)0.03952 (18)
S30.28393 (7)0.64232 (7)0.55098 (5)0.03611 (17)
S40.22813 (8)0.85040 (8)0.80525 (5)0.04221 (18)
S5−0.14480 (9)0.82971 (9)0.62019 (6)0.04559 (19)
N10.0187 (3)0.6694 (2)0.30088 (18)0.0370 (4)
H10.00900.65100.38030.044*
N2−0.1092 (3)0.7742 (3)0.86906 (19)0.0440 (5)
H2−0.03580.76390.93840.053*
C1−0.1562 (3)0.6703 (4)0.2139 (3)0.0485 (6)
H1A−0.13700.77990.18370.073*
H1B−0.26190.66040.26340.073*
H1C−0.18510.57130.13690.073*
C20.1897 (3)0.6948 (3)0.26569 (19)0.0333 (4)
C30.3067 (3)0.8671 (3)0.6478 (2)0.0390 (5)
H3A0.44020.93590.66360.047*
H3B0.22750.92670.59830.047*
C4−0.0280 (3)0.8118 (3)0.7646 (2)0.0346 (4)
C5−0.3151 (3)0.7494 (4)0.8732 (3)0.0488 (6)
H5A−0.34320.86380.89780.073*
H5B−0.34980.68120.93880.073*
H5C−0.38810.68670.78560.073*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0507 (4)0.0674 (4)0.0306 (3)0.0158 (3)0.0153 (2)0.0206 (3)
S20.0326 (3)0.0578 (4)0.0331 (3)0.0132 (2)0.0107 (2)0.0168 (3)
S30.0393 (3)0.0427 (3)0.0300 (3)0.0103 (2)0.0079 (2)0.0157 (2)
S40.0366 (3)0.0623 (4)0.0270 (3)0.0115 (3)0.0030 (2)0.0107 (3)
S50.0446 (3)0.0627 (4)0.0328 (3)0.0181 (3)0.0012 (2)0.0168 (3)
N10.0357 (9)0.0483 (10)0.0304 (8)0.0113 (8)0.0081 (7)0.0145 (8)
N20.0385 (10)0.0645 (12)0.0333 (9)0.0154 (9)0.0056 (8)0.0187 (9)
C10.0379 (13)0.0657 (15)0.0452 (12)0.0161 (11)0.0032 (10)0.0193 (12)
C20.0388 (11)0.0358 (9)0.0276 (9)0.0105 (8)0.0077 (8)0.0104 (8)
C30.0413 (11)0.0417 (11)0.0331 (10)0.0045 (9)0.0093 (9)0.0116 (9)
C40.0385 (11)0.0382 (10)0.0290 (9)0.0136 (8)0.0061 (8)0.0073 (8)
C50.0395 (13)0.0686 (16)0.0417 (12)0.0180 (12)0.0101 (10)0.0137 (12)

Geometric parameters (Å, °)

S1—C21.6671 (18)N2—C51.456 (3)
S2—C21.767 (2)N2—H20.8600
S2—S32.0364 (8)C1—H1A0.9600
S3—C31.816 (2)C1—H1B0.9600
S4—C41.782 (2)C1—H1C0.9600
S4—C31.787 (2)C3—H3A0.9700
S5—C41.655 (2)C3—H3B0.9700
N1—C21.306 (3)C5—H5A0.9600
N1—C11.453 (3)C5—H5B0.9600
N1—H10.8600C5—H5C0.9600
N2—C41.328 (3)
C2—S2—S3105.99 (7)S1—C2—S2113.24 (12)
C3—S3—S2101.85 (7)S4—C3—S3107.88 (10)
C4—S4—C3103.25 (10)S4—C3—H3A110.1
C2—N1—C1123.90 (17)S3—C3—H3A110.1
C2—N1—H1118.0S4—C3—H3B110.1
C1—N1—H1118.0S3—C3—H3B110.1
C4—N2—C5123.93 (18)H3A—C3—H3B108.4
C4—N2—H2118.0N2—C4—S5125.43 (17)
C5—N2—H2118.0N2—C4—S4109.93 (14)
N1—C1—H1A109.5S5—C4—S4124.59 (12)
N1—C1—H1B109.5N2—C5—H5A109.5
H1A—C1—H1B109.5N2—C5—H5B109.5
N1—C1—H1C109.5H5A—C5—H5B109.5
H1A—C1—H1C109.5N2—C5—H5C109.5
H1B—C1—H1C109.5H5A—C5—H5C109.5
N1—C2—S1127.70 (16)H5B—C5—H5C109.5
N1—C2—S2119.06 (14)
C2—S2—S3—C3−90.13 (11)S2—S3—C3—S4−177.57 (9)
C1—N1—C2—S1−0.4 (3)C5—N2—C4—S5−2.4 (3)
C1—N1—C2—S2179.97 (18)C5—N2—C4—S4175.1 (2)
S3—S2—C2—N1−0.01 (19)C3—S4—C4—N2172.23 (16)
S3—S2—C2—S1−179.71 (9)C3—S4—C4—S5−10.31 (17)
C4—S4—C3—S3−83.86 (14)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···S30.862.503.073 (2)125
N1—H1···S3i0.863.023.595 (2)127
N2—H2···S1ii0.862.673.515 (2)168

Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2358).

References

  • Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst.37, 335–338.
  • Brandenburg, K. (2007). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Cox, M. J. & Tiekink, E. R. T. (1999). Z. Kristallogr.214, 486–491.
  • Liu, Y. Y. & Bao, W. L. (2007). Tetrahedron Lett.48, 4785–4788.
  • Nair, P. S., Radhakrishan, T., Revaprasadu, N., Kolawole, G. A. & O’ Brien, P. (2002). J. Mater. Chem.12, 2722–2725.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stoe & Cie (2002). X-AREA and X-RED32 Stoe & Cie, Darmstadt, Germany.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography