Bis(N-methyl-N-phenyl­thio­carbamoyl) di­sulfide

In the title mol­ecule, C₁₆H₁₆N₂S₄, the two di­thio­carbamate groups, which are perpendicular to each other, are linked by an S-S bond. The di­thio­carbamate groups adopt a trans-planar conformation and form a dihedral angle of 89.75 (8)° with each other. The phenyl rings make dihedral angles of 77.3 (2) and 89.2 (2)° with the di­thio­carbamate plane. The C-N bonds in the di­thio­carbamate groups show partial double-bond character.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.071
• wR factor = 0.216
• Data-to-parameter ratio = 21.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Bis(dialkylthiocarbamoyl) disulfide compounds are highly effective in breaking the dormancy of plant seeds, bulbs and tubers. These compounds can be used as herbicides or in the cultivation of crop plants during the off-season (Hideo et al., 1974). Gasoline base-stocks are blended with 0.001–0.500% by weight of these compounds to obtain stable compounds suitable for long-term storage without sludge deposition (Kenichiro & Michiro, 1992). They are also used as additives to electrolytes for secondary lithium batteries. The use of these electrolytes prevents the growth of Li dendrites and results in a long life-cycle for the batteries [Masayuki, 1996].

The X-ray crystal structure of the title compound, (I) (Fig. 1), confirms that the molecules consists of two N-methyl-N-phenyldithiocarbamate units linked by an S—S bond. The two planar dithiocarbamate units are oriented perpendicular to each other, with a dihedral angle of 89.75 (8)° between them. The methyl C atoms are nearly coplanar with the NCSS units, with deviations of 0.010 (4) and 0.013 (5) Å. The bridging S2—S3 moiety is almost in the plane of each S₂CNMe subunit (Table 1). The two phenyl rings make anglesof 77.26 (17) and 89.17 (19)° with each S₂CNMe plane. The shorter N1—C8 and N2—C9 bond distances in the dithiocarbamate units are indicative of considerable double-bond character. The S—C, S═C and C—N bond distances are comparable with those observed in the related structures (Sharma et al., 1991; Gimeno et al., 1996; Jian et al., 1999). Short S2···C1 [2.828 (3) Å], S2···C9 [2.980 (4) Å], S3···C11 [2.820 (4) Å], S3···C8 [2.985 (4) Å], S1···C7 [3.071 (4) Å] and S4···C10 [3.044 (5) Å] intramolecular contacts are observed in this structure.

S2. Experimental

To a heated aqueous solution of sodium N-methyl-N-phenyldithiocarbamate was added, with stirring, a solution of lanthanum chloride. The white precipitate was collected by filtration. Colourless block crystals were obtained by recrystallizing the deposit from a solution of EtOH.

Computing details

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 and PLATON (Spek, 1990).

Figures

Fig. 1. The structure of the title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Bis(N-methyl-N-phenylthiocarbamoyl) disulfide

Crystal data

C16H16N2S4	F(000) = 760
Mr = 364.55	Dx = 1.355 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.6233 (2) Å	Cell parameters from 5529 reflections
b = 10.7356 (2) Å	θ = 2.1–28.3°
c = 17.2999 (3) Å	µ = 0.53 mm^−1
β = 91.624 (1)°	T = 293 K
V = 1786.57 (6) Å^3	Block, colourless
Z = 4	0.26 × 0.22 × 0.08 mm

Data collection

Siemens SMART CCD area-detector diffractometer	4353 independent reflections
Radiation source: fine-focus sealed tube	2395 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.083
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 2.1°
ω scans	h = −12→11
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −14→12
Tmin = 0.875, Tmax = 0.959	l = −23→22
12183 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.071	H-atom parameters constrained
wR(F^2) = 0.216	w = 1/[σ^2(Fo^2) + (0.1095P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
4353 reflections	Δρmax = 0.46 e Å^−3
202 parameters	Δρmin = −0.78 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (2)

Special details

Experimental. The data collection covered a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible.

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.25051 (11)	0.34438 (12)	0.04194 (7)	0.0637 (4)
S2	0.04187 (11)	0.17521 (9)	0.12010 (6)	0.0516 (3)
S3	0.20733 (11)	0.17675 (9)	0.19393 (7)	0.0544 (3)
S4	0.02917 (11)	0.39421 (11)	0.24788 (7)	0.0576 (4)
N1	−0.0058 (3)	0.2965 (3)	−0.00920 (18)	0.0416 (7)
N2	0.2791 (3)	0.3310 (3)	0.30389 (19)	0.0489 (8)
C1	−0.1431 (3)	0.2432 (3)	−0.0027 (2)	0.0396 (8)
C2	−0.2375 (4)	0.3001 (4)	0.0453 (3)	0.0578 (11)
H2A	−0.2110	0.3683	0.0754	0.069*
C3	−0.3713 (4)	0.2541 (4)	0.0477 (3)	0.0596 (11)
H3A	−0.4350	0.2906	0.0802	0.071*
C4	−0.4106 (4)	0.1541 (4)	0.0020 (3)	0.0576 (11)
H4A	−0.5013	0.1243	0.0031	0.069*
C5	−0.3179 (5)	0.0990 (4)	−0.0444 (3)	0.0664 (13)
H5A	−0.3454	0.0312	−0.0746	0.080*
C6	−0.1822 (5)	0.1424 (4)	−0.0473 (3)	0.0549 (11)
H6A	−0.1187	0.1039	−0.0791	0.066*
C7	0.0140 (4)	0.3707 (4)	−0.0799 (2)	0.0586 (11)
H7A	0.1115	0.3849	−0.0865	0.088*
H7B	−0.0328	0.4492	−0.0753	0.088*
H7C	−0.0237	0.3264	−0.1238	0.088*
C8	0.0957 (4)	0.2793 (3)	0.0443 (2)	0.0427 (9)
C9	0.1732 (4)	0.3106 (3)	0.2536 (2)	0.0412 (8)
C10	0.2710 (5)	0.4287 (5)	0.3631 (3)	0.0773 (15)
H10A	0.3625	0.4601	0.3749	0.116*
H10B	0.2322	0.3945	0.4090	0.116*
H10C	0.2129	0.4953	0.3439	0.116*
C11	0.4071 (4)	0.2607 (4)	0.3044 (2)	0.0476 (9)
C12	0.5154 (5)	0.3017 (6)	0.2612 (3)	0.0783 (15)
H12A	0.5059	0.3727	0.2307	0.094*
C13	0.6409 (5)	0.2346 (6)	0.2637 (4)	0.0950 (19)
H13A	0.7144	0.2598	0.2337	0.114*
C14	0.6549 (6)	0.1340 (6)	0.3096 (3)	0.0847 (18)
H14A	0.7384	0.0904	0.3115	0.102*
C15	0.5493 (6)	0.0962 (5)	0.3524 (3)	0.0835 (17)
H15A	0.5608	0.0272	0.3845	0.100*
C16	0.4233 (5)	0.1583 (4)	0.3499 (3)	0.0640 (12)
H16A	0.3500	0.1300	0.3791	0.077*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0288 (5)	0.0857 (9)	0.0762 (7)	−0.0162 (5)	−0.0046 (5)	−0.0068 (6)
S2	0.0406 (6)	0.0450 (6)	0.0680 (6)	−0.0074 (4)	−0.0201 (5)	0.0020 (5)
S3	0.0453 (6)	0.0449 (6)	0.0717 (7)	0.0123 (4)	−0.0236 (5)	−0.0122 (5)
S4	0.0366 (6)	0.0642 (7)	0.0715 (7)	0.0171 (5)	−0.0079 (5)	−0.0028 (6)
N1	0.0275 (15)	0.0461 (17)	0.0511 (15)	−0.0045 (13)	−0.0020 (14)	0.0000 (15)
N2	0.0403 (18)	0.051 (2)	0.0545 (17)	0.0127 (15)	−0.0145 (15)	−0.0141 (16)
C1	0.0243 (17)	0.042 (2)	0.0521 (18)	−0.0032 (15)	−0.0099 (15)	0.0044 (17)
C2	0.036 (2)	0.047 (2)	0.090 (3)	−0.0049 (18)	−0.003 (2)	−0.007 (2)
C3	0.036 (2)	0.067 (3)	0.076 (3)	0.003 (2)	0.004 (2)	0.000 (3)
C4	0.033 (2)	0.066 (3)	0.073 (3)	−0.0161 (19)	−0.016 (2)	0.018 (2)
C5	0.059 (3)	0.055 (3)	0.084 (3)	−0.028 (2)	−0.013 (3)	0.000 (2)
C6	0.047 (2)	0.049 (2)	0.068 (3)	−0.0102 (19)	0.003 (2)	−0.011 (2)
C7	0.042 (2)	0.066 (3)	0.068 (2)	−0.012 (2)	−0.005 (2)	0.013 (2)
C8	0.0288 (18)	0.041 (2)	0.058 (2)	0.0007 (15)	−0.0030 (17)	−0.0158 (18)
C9	0.0330 (19)	0.043 (2)	0.0482 (17)	0.0050 (16)	0.0011 (16)	0.0005 (17)
C10	0.071 (3)	0.071 (3)	0.088 (3)	0.026 (3)	−0.031 (3)	−0.034 (3)
C11	0.033 (2)	0.047 (2)	0.062 (2)	0.0095 (17)	−0.0154 (18)	−0.010 (2)
C12	0.048 (3)	0.096 (4)	0.090 (4)	0.003 (3)	−0.003 (3)	0.022 (3)
C13	0.046 (3)	0.135 (5)	0.105 (4)	0.010 (3)	0.012 (3)	0.010 (4)
C14	0.054 (3)	0.122 (5)	0.076 (3)	0.038 (3)	−0.022 (3)	−0.038 (4)
C15	0.090 (4)	0.067 (3)	0.092 (4)	0.037 (3)	−0.039 (3)	−0.019 (3)
C16	0.055 (3)	0.055 (3)	0.082 (3)	0.012 (2)	−0.012 (2)	−0.005 (2)

Geometric parameters (Å, º)

S1—C8	1.647 (4)	C1—C2	1.390 (5)
S2—C8	1.810 (4)	C2—C3	1.380 (5)
S2—S3	2.0128 (14)	C3—C4	1.380 (6)
S3—C9	1.805 (4)	C4—C5	1.353 (6)
S4—C9	1.652 (4)	C5—C6	1.389 (6)
N1—C8	1.339 (5)	C11—C16	1.358 (6)
N1—C1	1.447 (4)	C11—C12	1.372 (6)
N1—C7	1.477 (5)	C12—C13	1.406 (7)
N2—C9	1.339 (5)	C13—C14	1.345 (8)
N2—C11	1.444 (5)	C14—C15	1.338 (8)
N2—C10	1.469 (5)	C15—C16	1.383 (6)
C1—C6	1.376 (5)
C8—S2—S3	102.54 (12)	C1—C6—C5	119.1 (4)
C9—S3—S2	102.49 (13)	N1—C8—S1	124.5 (3)
C8—N1—C1	122.8 (3)	N1—C8—S2	111.6 (3)
C8—N1—C7	122.5 (3)	S1—C8—S2	123.9 (2)
C1—N1—C7	114.7 (3)	N2—C9—S4	124.9 (3)
C9—N2—C11	123.5 (3)	N2—C9—S3	110.8 (3)
C9—N2—C10	121.0 (3)	S4—C9—S3	124.3 (2)
C11—N2—C10	115.5 (3)	C16—C11—C12	119.9 (4)
C6—C1—C2	120.5 (4)	C16—C11—N2	120.7 (4)
C6—C1—N1	120.2 (3)	C12—C11—N2	119.3 (4)
C2—C1—N1	119.1 (3)	C11—C12—C13	118.9 (5)
C3—C2—C1	119.1 (4)	C14—C13—C12	120.1 (5)
C4—C3—C2	120.1 (4)	C15—C14—C13	120.4 (5)
C5—C4—C3	120.4 (4)	C14—C15—C16	121.0 (5)
C4—C5—C6	120.8 (4)	C11—C16—C15	119.7 (5)
C8—S2—S3—C9	86.18 (18)	C11—N2—C9—S4	−176.2 (3)
C8—N1—C1—C6	−105.2 (4)	C10—N2—C9—S4	3.8 (6)
C7—N1—C1—C6	74.4 (5)	C11—N2—C9—S3	5.0 (5)
C8—N1—C1—C2	79.1 (5)	C10—N2—C9—S3	−175.0 (3)
C7—N1—C1—C2	−101.3 (4)	S2—S3—C9—N2	−176.0 (2)
C6—C1—C2—C3	0.1 (6)	S2—S3—C9—S4	5.2 (3)
N1—C1—C2—C3	175.8 (4)	C9—N2—C11—C16	−92.7 (5)
C1—C2—C3—C4	−1.0 (7)	C10—N2—C11—C16	87.2 (5)
C2—C3—C4—C5	1.2 (7)	C9—N2—C11—C12	90.3 (5)
C3—C4—C5—C6	−0.5 (7)	C10—N2—C11—C12	−89.7 (5)
C2—C1—C6—C5	0.6 (6)	C16—C11—C12—C13	1.3 (8)
N1—C1—C6—C5	−175.1 (4)	N2—C11—C12—C13	178.3 (5)
C4—C5—C6—C1	−0.4 (7)	C11—C12—C13—C14	−1.8 (9)
C1—N1—C8—S1	−176.4 (3)	C12—C13—C14—C15	0.7 (9)
C7—N1—C8—S1	4.1 (5)	C13—C14—C15—C16	0.9 (8)
C1—N1—C8—S2	3.7 (4)	C12—C11—C16—C15	0.3 (7)
C7—N1—C8—S2	−175.9 (3)	N2—C11—C16—C15	−176.7 (4)
S3—S2—C8—N1	−176.3 (2)	C14—C15—C16—C11	−1.4 (8)
S3—S2—C8—S1	3.7 (3)