[(Methyl­carbamothio­yl)disulfan­yl]methyl N-methyl­carbamodithio­ate

Khan, H.; Aziz, M.; Neuhausen, C.; Murtaza, G.; Shaheen, F.

doi:10.1107/S160053681003833X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2671

doi:10.1107/S160053681003833X

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[(Methylcarbamothioyl)disulfanyl]methyl N-methylcarbamodithioate

Hizbullah Khan,^a ^* Muhammad Aziz,^b Christine Neuhausen,^c Ghulam Murtaza ^a and Farkhanda Shaheen ^a

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan, ^bDepartment of Chemistry, University of Science and Technology, Mirpur AJK, Pakistan, and ^cLaboratoire de Cristallographie, Ecole Polytechnique Fédérale de Lausanne, Switzerland
^*Correspondence e-mail: hizbmarwat@yahoo.com

(Received 19 August 2010; accepted 25 September 2010; online 30 September 2010)

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 ); Liu & Bao (2007 ); Nair et al. (2002 ).

Experimental

Crystal data

C₅H₁₀N₂S₅
M_r = 258.45
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.103
S = 1.15
2077 reflections
111 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: X-AREA (Stoe & Cie, 2002 ); cell refinement: X-RED32 (Stoe & Cie, 2002); data reduction: X-RED32; 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 ).

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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%.

Computing details top

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).

Figures top

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

[(Methylcarbamothioyl)disulfanyl]methyl N-methylcarbamodithioate top

Crystal data top

C₅H₁₀N₂S₅	V = 546.0 (2) Å³
M_r = 258.45	Z = 2
Triclinic, P1	F(000) = 268
a = 7.188 (1) Å	D_x = 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

Data collection top

Stoe IPDS diffractometer	1924 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.101
Graphite monochromator	θ_max = 26.4°, θ_min = 4.1°
ω scans	h = −8→8
4080 measured reflections	k = −9→9
2077 independent reflections	l = −12→12

Refinement top

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(F_o²) + (0.0496P)² + 0.0335P] where P = (F_o² + 2F_c²)/3
2077 reflections	(Δ/σ)_max = 0.001
111 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₅H₁₀N₂S₅	γ = 102.74 (3)°
M_r = 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)°

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.15	Δρ_max = 0.53 e Å⁻³
2077 reflections	Δρ_min = −0.37 e Å⁻³
111 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	0.24777 (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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Experimental details

Crystal data
Chemical formula	C₅H₁₀N₂S₅
M_r	258.45
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.188 (1), 7.884 (2), 10.219 (2)
α, β, γ (°)	101.23 (3), 96.85 (3), 102.74 (3)
V (Å³)	546.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.01
Crystal size (mm)	0.30 × 0.11 × 0.10

Data collection
Diffractometer	Stoe IPDS diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4080, 2077, 1924
R_int	0.101
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.103, 1.15
No. of reflections	2077
No. of parameters	111
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.37

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2007), enCIFer (Allen et al., 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S3	0.86	2.50	3.073 (2)	125.0
N1—H1···S3ⁱ	0.86	3.02	3.595 (2)	126.5
N2—H2···S1ⁱⁱ	0.86	2.67	3.515 (2)	167.8

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

Acknowledgements

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

References

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