Acta Cryst. (2010). E66, o2671 [ doi:10.1107/S160053681003833X ]
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-HS hydrogen bond also occurs.
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%.
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).
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-RED32 (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2007); software used to prepare material for publication: enCIFer (Allen et al., 2004).
![[Figure 1]](./om2358fig1thm.gif)
| Fig. 1. The molecular structure with atom labels and 50% probability displacement ellipsoids for non-H atoms. |
| C5H10N2S5 | V = 546.0 (2) Å3 |
| Mr = 258.45 | Z = 2 |
| Triclinic, P1 | F(000) = 268 |
| a = 7.188 (1) Å | Dx = 1.572 Mg m−3 |
| b = 7.884 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
| c = 10.219 (2) Å | µ = 1.01 mm−1 |
| α = 101.23 (3)° | T = 293 K |
| β = 96.85 (3)° | Needle, yellow |
| γ = 102.74 (3)° | 0.30 × 0.11 × 0.10 mm |
| Stoe IPDS diffractometer | 1924 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.101 |
| graphite | θmax = 26.4°, θmin = 4.1° |
| ω scans | h = −8→8 |
| 4080 measured reflections | k = −9→9 |
| 2077 independent reflections | l = −12→12 |
| 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.103 | H-atom parameters constrained |
| S = 1.15 | w = 1/[σ2(Fo2) + (0.0496P)2 + 0.0335P] where P = (Fo2 + 2Fc2)/3 |
| 2077 reflections | (Δ/σ)max = 0.001 |
| 111 parameters | Δρmax = 0.53 e Å−3 |
| 0 restraints | Δρmin = −0.37 e Å−3 |
| C5H10N2S5 | γ = 102.74 (3)° |
| Mr = 258.45 | V = 546.0 (2) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.188 (1) Å | Mo Kα radiation |
| b = 7.884 (2) Å | µ = 1.01 mm−1 |
| c = 10.219 (2) Å | T = 293 K |
| α = 101.23 (3)° | 0.30 × 0.11 × 0.10 mm |
| β = 96.85 (3)° |
| Stoe IPDS diffractometer | 1924 reflections with I > 2σ(I) |
| 4080 measured reflections | Rint = 0.101 |
| 2077 independent reflections | θmax = 26.4° |
| R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
| wR(F2) = 0.103 | Δρmax = 0.53 e Å−3 |
| S = 1.15 | Δρmin = −0.37 e Å−3 |
| 2077 reflections | Absolute structure: ? |
| 111 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.24777 (9) | 0.73176 (9) | 0.11879 (5) | 0.04736 (19) | |
| S2 | 0.39011 (7) | 0.69015 (8) | 0.38202 (5) | 0.03952 (18) | |
| S3 | 0.28393 (7) | 0.64232 (7) | 0.55098 (5) | 0.03611 (17) | |
| S4 | 0.22813 (8) | 0.85040 (8) | 0.80525 (5) | 0.04221 (18) | |
| S5 | −0.14480 (9) | 0.82971 (9) | 0.62019 (6) | 0.04559 (19) | |
| N1 | 0.0187 (3) | 0.6694 (2) | 0.30088 (18) | 0.0370 (4) | |
| H1 | 0.0090 | 0.6510 | 0.3803 | 0.044* | |
| N2 | −0.1092 (3) | 0.7742 (3) | 0.86906 (19) | 0.0440 (5) | |
| H2 | −0.0358 | 0.7639 | 0.9384 | 0.053* | |
| C1 | −0.1562 (3) | 0.6703 (4) | 0.2139 (3) | 0.0485 (6) | |
| H1A | −0.1370 | 0.7799 | 0.1837 | 0.073* | |
| H1B | −0.2619 | 0.6604 | 0.2634 | 0.073* | |
| H1C | −0.1851 | 0.5713 | 0.1369 | 0.073* | |
| C2 | 0.1897 (3) | 0.6948 (3) | 0.26569 (19) | 0.0333 (4) | |
| C3 | 0.3067 (3) | 0.8671 (3) | 0.6478 (2) | 0.0390 (5) | |
| H3A | 0.4402 | 0.9359 | 0.6636 | 0.047* | |
| H3B | 0.2275 | 0.9267 | 0.5983 | 0.047* | |
| 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 | −0.3432 | 0.8638 | 0.8978 | 0.073* | |
| H5B | −0.3498 | 0.6812 | 0.9388 | 0.073* | |
| H5C | −0.3881 | 0.6867 | 0.7856 | 0.073* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0507 (4) | 0.0674 (4) | 0.0306 (3) | 0.0158 (3) | 0.0153 (2) | 0.0206 (3) |
| S2 | 0.0326 (3) | 0.0578 (4) | 0.0331 (3) | 0.0132 (2) | 0.0107 (2) | 0.0168 (3) |
| S3 | 0.0393 (3) | 0.0427 (3) | 0.0300 (3) | 0.0103 (2) | 0.0079 (2) | 0.0157 (2) |
| S4 | 0.0366 (3) | 0.0623 (4) | 0.0270 (3) | 0.0115 (3) | 0.0030 (2) | 0.0107 (3) |
| S5 | 0.0446 (3) | 0.0627 (4) | 0.0328 (3) | 0.0181 (3) | 0.0012 (2) | 0.0168 (3) |
| N1 | 0.0357 (9) | 0.0483 (10) | 0.0304 (8) | 0.0113 (8) | 0.0081 (7) | 0.0145 (8) |
| N2 | 0.0385 (10) | 0.0645 (12) | 0.0333 (9) | 0.0154 (9) | 0.0056 (8) | 0.0187 (9) |
| C1 | 0.0379 (13) | 0.0657 (15) | 0.0452 (12) | 0.0161 (11) | 0.0032 (10) | 0.0193 (12) |
| C2 | 0.0388 (11) | 0.0358 (9) | 0.0276 (9) | 0.0105 (8) | 0.0077 (8) | 0.0104 (8) |
| C3 | 0.0413 (11) | 0.0417 (11) | 0.0331 (10) | 0.0045 (9) | 0.0093 (9) | 0.0116 (9) |
| C4 | 0.0385 (11) | 0.0382 (10) | 0.0290 (9) | 0.0136 (8) | 0.0061 (8) | 0.0073 (8) |
| C5 | 0.0395 (13) | 0.0686 (16) | 0.0417 (12) | 0.0180 (12) | 0.0101 (10) | 0.0137 (12) |
| S1—C2 | 1.6671 (18) | N2—C5 | 1.456 (3) |
| S2—C2 | 1.767 (2) | N2—H2 | 0.8600 |
| S2—S3 | 2.0364 (8) | C1—H1A | 0.9600 |
| S3—C3 | 1.816 (2) | C1—H1B | 0.9600 |
| S4—C4 | 1.782 (2) | C1—H1C | 0.9600 |
| S4—C3 | 1.787 (2) | C3—H3A | 0.9700 |
| S5—C4 | 1.655 (2) | C3—H3B | 0.9700 |
| N1—C2 | 1.306 (3) | C5—H5A | 0.9600 |
| N1—C1 | 1.453 (3) | C5—H5B | 0.9600 |
| N1—H1 | 0.8600 | C5—H5C | 0.9600 |
| N2—C4 | 1.328 (3) | ||
| C2—S2—S3 | 105.99 (7) | S1—C2—S2 | 113.24 (12) |
| C3—S3—S2 | 101.85 (7) | S4—C3—S3 | 107.88 (10) |
| C4—S4—C3 | 103.25 (10) | S4—C3—H3A | 110.1 |
| C2—N1—C1 | 123.90 (17) | S3—C3—H3A | 110.1 |
| C2—N1—H1 | 118.0 | S4—C3—H3B | 110.1 |
| C1—N1—H1 | 118.0 | S3—C3—H3B | 110.1 |
| C4—N2—C5 | 123.93 (18) | H3A—C3—H3B | 108.4 |
| C4—N2—H2 | 118.0 | N2—C4—S5 | 125.43 (17) |
| C5—N2—H2 | 118.0 | N2—C4—S4 | 109.93 (14) |
| N1—C1—H1A | 109.5 | S5—C4—S4 | 124.59 (12) |
| N1—C1—H1B | 109.5 | N2—C5—H5A | 109.5 |
| H1A—C1—H1B | 109.5 | N2—C5—H5B | 109.5 |
| N1—C1—H1C | 109.5 | H5A—C5—H5B | 109.5 |
| H1A—C1—H1C | 109.5 | N2—C5—H5C | 109.5 |
| H1B—C1—H1C | 109.5 | H5A—C5—H5C | 109.5 |
| N1—C2—S1 | 127.70 (16) | H5B—C5—H5C | 109.5 |
| N1—C2—S2 | 119.06 (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—S2 | 179.97 (18) | C5—N2—C4—S4 | 175.1 (2) |
| S3—S2—C2—N1 | −0.01 (19) | C3—S4—C4—N2 | 172.23 (16) |
| S3—S2—C2—S1 | −179.71 (9) | C3—S4—C4—S5 | −10.31 (17) |
| C4—S4—C3—S3 | −83.86 (14) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···S3 | 0.86 | 2.50 | 3.073 (2) | 125 |
| N1—H1···S3i | 0.86 | 3.02 | 3.595 (2) | 127 |
| N2—H2···S1ii | 0.86 | 2.67 | 3.515 (2) | 168 |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···S3 | 0.86 | 2.50 | 3.073 (2) | 125 |
| N1—H1···S3i | 0.86 | 3.02 | 3.595 (2) | 127 |
| N2—H2···S1ii | 0.86 | 2.67 | 3.515 (2) | 168 |
| Symmetry codes: (i) −x, −y+1, −z+1; (ii) x, y, z+1. |
The authors thank the Higher Education Commission of Pakistan (HEC) for financial support.
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.
Stoe & Cie (2002). X-AREA and X-RED32. Stoe & Cie, Darmstadt, Germany.
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).