3-Methyl-5-methyl­sulfanyl-1,3,4-thia­diazole-2(3H)-thione

Suarez, S.A.; Hazari, S.K.S.; Ganguly, B.; Doctorovich, F.; Roy, T.G.; Baggio, R.

doi:10.1107/S1600536812040147

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Pages o3045-o3046

https://doi.org/10.1107/S1600536812040147

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3-Methyl-5-methylsulfanyl-1,3,4-thiadiazole-2(3H)-thione

Sebastian A. Suarez,^a ^* Saroj K. S. Hazari,^b Biplab Ganguly,^b Fabio Doctorovich,^a Tapashi G. Roy ^b and Ricardo Baggio ^c

^aDepartamento de Química Inorgánica, Analítica y Química, Física/INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Argentina, ^bUniversity of Chittagong, Chittagong 4331, Bangladesh, and ^cGerencia de Investigación y Aplicaciones, Centro Atómico Constituyentes, Comisión Nacional de Energía Atómica, Buenos Aires, Argentina
^*Correspondence e-mail: doctorovich@qi.fcen.uba.ar

(Received 18 September 2012; accepted 21 September 2012; online 29 September 2012)

The title compound, C₄H₆N₂S₃, has two very similar molecules per asymmetric unit. The nine non-H atoms in each molecule are coplanar, both having comparable r.m.s. deviations of 0.002 Å. The main interest in the rather simple structure resides in a survey of very weak (in some cases, borderline) non-bonding interactions of various kinds, viz. S⋯S, C—H⋯π, π–π [centroid–centroid distance = 3.8958 (13) Å] and C—S⋯π [3.7271 (11) Å], which act as the major driving force for the arrangement of molecules in the structure. The role of long, though highly directional, S⋯S contacts (d > 3.60 Å), and their relevance to the stability of the structure is discussed.

Related literature

For the synthesis and characterization of the title compound, see: Espinosa et al. (2010 ); Thorn (1960 ). For the reactivity of thiadiazole, see: Espinosa et al. (2010). For significance of weak S⋯S interactions and for the role of weak interactions in the absence of stronger ones, see: Allen (2002 ); Bats (1976 ); Bondi (1964 ); Desiraju & Steiner (1999 ); Mrozek et al. (2000 ); Iwaoka & Isozumi (2012 ).

Experimental

Crystal data

C₄H₆N₂S₃
M_r = 178.30
Monoclinic, P 2₁ /c
a = 9.3505 (4) Å
b = 22.4118 (9) Å
c = 7.6682 (5) Å
β = 106.661 (5)°
V = 1539.50 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 295 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Gemini CCD S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.81, T_max = 0.84
32965 measured reflections
3821 independent reflections
2690 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.102
S = 1.04
3821 reflections
167 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Selected interatomic distances (Å)

S3⋯S2ⁱ	3.6438 (10)
S2⋯S2ⁱⁱ	3.6319 (9)
S6⋯S5ⁱⁱⁱ	3.7189 (11)
S3⋯S4^iv	3.3671 (10)
S1⋯S6^v	3.3621 (10)
S1⋯S5^iv	3.8332 (11)
S2⋯S4^v	3.8778 (10)
Symmetry codes: (i) x+1, y, z; (ii) -x, -y+1, -z+1; (iii) x-1, y, z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
C—H⋯π interaction (Å, °)

Cg1 is the centroid of the C1,C2,N1,N2,S1 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4C⋯Cg1^vi	0.96	2.86	3.589 (3)	134
Symmetry code: (vi) -x, -y+1, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812040147/zl2506sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812040147/zl2506Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812040147/zl2506Isup3.cml

checkCIF report

Comment top

During a systematic trial intended to synthesize a molybdenum(VI) complex of our interest (see experimental section for details) excellent crystals were obtained, at the time thought to correspond to the expected product. A straightforward crystal structure determination disclosed that the compound was in fact the rather simple heterocyclic title compound, C₄H₆N₂S₃ (Scheme 1), a readily available commercial product (Thorn, 1960; Espinosa et al., 2010), but the crystal structure of which had not been reported so far. Incidentally, the molecule has very little to do with any of the starting materials used, and the mechanism through which it could have been generated during the unsuccessful synthesis remains basically unclear (the point is further discussed in the experimental section). In addition to the rather expectable molecular information the study revealed a surprising collection of varied non-bonding interactions which affect the overall stability of the crystal structure, and to the analysis of which most of the following discussion will be devoted.

The asymmetric unit of the title compound includes two independent molecules (A and B) consisting of a 1,3,4-thiadiazole ring, with a methyl group attached at position 3 and a thiomethyl at position 5 (Figure 1). Both are essentially planar (max. deviations from planarity, 0.002 Å) but not parallel (dihedral angle: 14.87 (4)°).

The two independent molecules exhibit no significant differences between each other (RMS deviation from the L.S. fit: 0.0159 (3) Å, max. deviation: 0.026 (2) Å for the N1, N4 pair) nor show they deviations from commonly accepted values for either bond distances or angles (CSD, version 1.14, Allen, 2002). S—C bonds of different types are fairly distinct and present a remarkable homogeneity in both moieties, as assessed by the tight ranges displayed: <S—C_arom>: 1.734 (2) -1.738 (2); <S═C_arom>: 1.655 (2) -1.662 (2); <S—C_methyl>: 1.796 (3) -1.797 (3).

With the molecular details being basically unexceptional, the most interesting aspect of the structure resides in its packing: in this respect this is a good example of very weak forces (London's, dipole-induced dipole, etc.) expressed as a variety of usually borderline interactions of various types (S···S (Table 1); C—H···π (Table 2); π–π, C—S···π (Table 3)) which in the absence of stronger ones can become the basic synthons promoting molecular recognition and intermolecular interaction, and thus playing an essential constructive role in the crystal lattice (Desiraju & Steiner, 1999; Iwaoka & Isozumi, 2012 (and references therein)).

Contrasting with the similarities shown by the internal molecular geometries, the packing behavior for the two independent moieties is quite different, for what they will be analyzed separately, molecule A (C1—C2—C3—C4—N1—N2—S1—S2—S3) and molecule B (C5—C6—C7—C8—N3—N4—S4—S5—S6).

Molecule B is the most simple to describe. Fig 2a shows its disposition in the crystal structure: the most relevant B···B interaction is a π–π contact between neighboring aromatic rings (Table 3: Entry 1, hereafter summarized in the compact expression T3:E1). These contacts link molecules into columnar arrays running along [001]. The a unit cell translation generates parallel columns a.sin(β) apart (~ 9 Å), thus defining some kind of two-dimensional structures parallel to (010), at y ~0.25, 0.75 (Fig 2 b). A weak S···S contact (T1:E3) helps to connect the columns, though the strongest link is in fact mediated by the second substructure of A, through interactions of the B···A···B type to be discussed below.

As opposed to B, molecule A displays a complex survey of rather long (and correspondingly, weak) contacts, which are relevant as effective interactions could have been regarded with suspicion under normal circumstances. Inspection of Fig. 3a, however, contradicts this view: a striking directionality displayed, assisting the construction of a planar array parallel to (010), is apparent and suggests a cooperative effect of the otherwise very weak interactions involved. Fig 3a shows them in detail: two S···S (T1:E1,E2) (a); a C—H···π (T2:E1) (b) and a S···π (T3:E2) (c), contacts. All of them are extremely weak and, as stated, under normal circumstances, they would have been disregarded. Particularly interesting are those referred to as (a) above: they are borderline when commonly accepted standards were applied, viz., in the CSD the standard Van der Waal's radius for sulfur is given as 1.80 Å, which would create an upper threshold of 3.60 Å to this type of S···S interactions, with a statistical maximum centred at d=3.586 Å. Inspection of Fig 3a suggests, however, directionality in many S···S contacts with d > 3.60 Å, indicating a possible effect on the two-dimensional organization of the molecules in the solid state. The same can be assessed for the remaining two interactions (b) and (c). The conclusion is certainly not novel, (see, for instance, Desiraju and Steiner, 1999) and could be summarized in that very weak interactions in the presence of stronger, dominant ones can be safely disregarded but if in isolation and acting in a collective fashion they might strengthen each other, enhancing their overall effects to the extent to sustain well defined substructures, as in the present case.

Coming back to the structural description, A planes evolve parallel to, and midway from B ones, along (010) at y ~ 0.0, 0.50 (Fig 3 b). Both substructures are interconnected (Fig 4) by two shorter (stronger) and two longer (weaker) S···S contacts (T1:E4,E5 and T1:E6,E7, respectively). The final result is an extremely even spatial distribution of these cooperative interactions (Figs 2, 3 and 4) providing to the organization of a solid and stable three-dimensional structure.

Trying to assess the general significance of these weak S···S interactions we searched the CSD (Allen, 2002) looking for small molecules, closely related to the title compound. We ended up with two structures built around a 1,3,4-thiadiazole-2(3H)-thione ring, viz, 2,5-dimercapto-thiadiazole (Bats, 1976; (II)) and 2-thioxo-5-(ethylthio)-3H-1,3,4-thiadiazole. (Mrozek et al., 2000; (III)) which differ from the title compound just in the substitutents on the ring (Fig. 5). Even if the packing geometries are different, mainly affected by the diversity of the remaining donors and acceptors present, all three structures basically show a similar survey of S···S contacts with a clear directionality but longer than the usually accepted threshold. Table 4 shows the shortest S···S contacts in all three structures. We conclude that these similarities are in fact a trend, confirming the significance of the analyzed interactions.

Related literature top

For the synthesis and characterization of the title compound, see: Espinosa et al. (2010); Thorn (1960). For the reactivity of thiadiazole, see: Espinosa et al. (2010). For significance of weak S···S interactions and for the role of weak interactions in the absence of stronger ones, see: Allen (2002); Bats (1976); Bondi (1964); Desiraju & Steiner (1999); Mrozek et al. (2000); Iwaoka & Isozumi (2012).

Experimental top

As mentioned in the comment section, the formation of the title compound in crystalline form was a serendipitous process, the result of an unsuccesfull attempt to prepare a Mo(VI) complex with the Schiff base ligand N'-[bis-(4-amino-phenyl)-methylene]-N-methyl-hydrazinecarbodithioic acid methyl ester, (L) prepared by condensation of 4,4-diaminobenzophenone and N-methyl-S-methyldithiocarbazate. After a number of steps, a greenish product, initially presumed to be the L-Mo(VI) complex, but later confirmed to be the title compound, was obtained. Since it is hard to relate the small molecule obtained with any of the starting materials or with possible degradation products, the mechanism through which it could have been formed remains unclear, and for this reason we are including herein a detailed description of the steps taken during the synthesis process:

Step-1. Synthesis of L: A hot solution of 4,4'-diaminobenzophenone (10 mmol) in 40 ml absolute ethanol was mixed with a similar one of N-methyl-S-methyldithiocarbazate (10 mmol) in 40 ml of the same solvent. The mixture was refluxed for 6 hs on a water bath. After reducing the volume, an off white product appeared which was filtered off. This product was washed with ethanol several times (5 ml each wash) and dried in a vacuum desiccator over silica gel. Yield: 1.69 g;

Step-2. Attempted preparation of the dioxomolybdeum(VI) complex: Molybdenyl acetylacetonate [MoO₂(acac)₂] (3.27 g, 10 mmol) was dissolved in 40 ml dry ethanol, to which a hot solution of the Schiff base ligand, L, (3.26 g, 10 mmol) in 40 ml dry ethanol was added. The mixture was refluxed for 6 hs on a water bath. After reducing the volume and keeping standing overnight, a light greenish product appeared which was washed with ethanol several times and dried in a vacuum desiccator over silica gel.

Step-3. Crystallization: The product obtained in Step-2 was allowed to crystallize by slow evaporation from an ethanol-petroleum ether mixture (2:1 v/v, 10 ml ethanol: 5 ml petroleum ether) solution, to give green crystals, later identified as the title compound.

Structure description top

For the synthesis and characterization of the title compound, see: Espinosa et al. (2010); Thorn (1960). For the reactivity of thiadiazole, see: Espinosa et al. (2010). For significance of weak S···S interactions and for the role of weak interactions in the absence of stronger ones, see: Allen (2002); Bats (1976); Bondi (1964); Desiraju & Steiner (1999); Mrozek et al. (2000); Iwaoka & Isozumi (2012).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing the atom-labeling scheme and displacement ellipsoids at the 40% probability level.
	Fig. 2. Crystal packing for the B substructure. a) viewed along b. b) viewed along a. Dashed lines indicate π–π bonds (See Table 3 for details). Symmetry codes: (iii) x-1, y, z; (vii) x, 3/2-y, 1/2+z.
	Fig. 3. Crystal packing for the A substructure. a) viewed along b. b) viewed along a. Heavy dashed lines indicate S···π interactions; soft dashed lines indicate S···S interactions; dotted lines indicate C—H···π interactions; (See Tables 1, 2 and 3 for details). Symmetry codes: (i) x+1, y, z; (ii) -x, -y+1, -z+1; (vi) -x, -y+1, -z; (viii) 1-x, 1-y, 1-z.
	Fig. 4. Complete crystal packing viewed along c and showing only interactions between A and B substructures. Soft dashed lines indicate S···S interactions (See Tables 1 for details). Symmetry code: (iv) -x+1, y-1/2, -z+1/2 (v) -x, y-1/2, -z+1/2.
	Fig. 5. Molecular scheme of the three closely related structures compared in the paper.

3-Methyl-5-methylsulfanyl-1,3,4-thiadiazole-2(3H)-thione top

Crystal data top

C₄H₆N₂S₃	F(000) = 736
M_r = 178.30	D_x = 1.539 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6608 reflections
a = 9.3505 (4) Å	θ = 3.5–29.0°
b = 22.4118 (9) Å	µ = 0.88 mm⁻¹
c = 7.6682 (5) Å	T = 295 K
β = 106.661 (5)°	Prism, colourless
V = 1539.50 (14) Å³	0.3 × 0.2 × 0.2 mm
Z = 8

Data collection top

Oxford Diffraction Gemini CCD S Ultra diffractometer	3821 independent reflections
Radiation source: fine-focus sealed tube	2690 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ω scans, thick slices	θ_max = 29.1°, θ_min = 3.5°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −12→12
T_min = 0.81, T_max = 0.84	k = −30→29
32965 measured reflections	l = −10→10

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) = 0.102	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0398P)² + 0.5703P] where P = (F_o² + 2F_c²)/3
3821 reflections	(Δ/σ)_max = 0.001
167 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₄H₆N₂S₃	V = 1539.50 (14) Å³
M_r = 178.30	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.3505 (4) Å	µ = 0.88 mm⁻¹
b = 22.4118 (9) Å	T = 295 K
c = 7.6682 (5) Å	0.3 × 0.2 × 0.2 mm
β = 106.661 (5)°

Data collection top

Oxford Diffraction Gemini CCD S Ultra diffractometer	3821 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2690 reflections with I > 2σ(I)
T_min = 0.81, T_max = 0.84	R_int = 0.060
32965 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.04	Δρ_max = 0.25 e Å⁻³
3821 reflections	Δρ_min = −0.27 e Å⁻³
167 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
C3	0.3939 (3)	0.57279 (10)	0.1948 (4)	0.0553 (6)
H3A	0.4718	0.5836	0.3019	0.083*
H3B	0.3252	0.6054	0.159	0.083*
H3C	0.4366	0.5637	0.098	0.083*
C4	−0.1404 (3)	0.54132 (12)	0.2162 (4)	0.0595 (7)
H4A	−0.0915	0.5686	0.3112	0.089*
H4B	−0.2458	0.5414	0.2022	0.089*
H4C	−0.1228	0.5534	0.1041	0.089*
C7	0.0292 (3)	0.67498 (11)	0.0189 (4)	0.0588 (7)
H7A	−0.0033	0.6733	0.1267	0.088*
H7B	0.0849	0.6396	0.011	0.088*
H7C	−0.0561	0.6776	−0.0863	0.088*
C8	0.5833 (3)	0.70055 (13)	0.0599 (4)	0.0654 (7)
H8A	0.57	0.6818	0.1668	0.098*
H8B	0.6867	0.6988	0.0635	0.098*
H8C	0.5243	0.6801	−0.0464	0.098*
S3	0.55055 (7)	0.44639 (3)	0.29305 (10)	0.05657 (19)
S1	0.24366 (7)	0.42026 (3)	0.32098 (9)	0.04892 (17)
S2	−0.06774 (7)	0.46747 (3)	0.27437 (9)	0.05080 (17)
N1	0.3150 (2)	0.52053 (8)	0.2336 (3)	0.0406 (4)
N2	0.1669 (2)	0.52810 (8)	0.2290 (3)	0.0420 (4)
C1	0.3770 (2)	0.46736 (9)	0.2779 (3)	0.0404 (5)
C2	0.1153 (2)	0.47832 (10)	0.2715 (3)	0.0414 (5)
S6	−0.09695 (7)	0.80636 (3)	0.00218 (11)	0.0622 (2)
S4	0.22529 (7)	0.83027 (3)	0.03346 (10)	0.05732 (19)
S5	0.52524 (7)	0.77719 (3)	0.05225 (10)	0.0598 (2)
N3	0.1238 (2)	0.72729 (8)	0.0269 (3)	0.0432 (4)
N4	0.2722 (2)	0.71785 (8)	0.0383 (3)	0.0469 (5)
C5	0.0747 (2)	0.78324 (10)	0.0200 (3)	0.0427 (5)
C6	0.3387 (3)	0.76844 (10)	0.0417 (3)	0.0445 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.0555 (15)	0.0384 (13)	0.0799 (18)	−0.0036 (11)	0.0321 (14)	0.0124 (12)
C4	0.0447 (14)	0.0685 (17)	0.0683 (17)	0.0017 (12)	0.0212 (13)	0.0040 (13)
C7	0.0499 (14)	0.0406 (13)	0.0840 (19)	−0.0117 (11)	0.0164 (13)	−0.0036 (12)
C8	0.0453 (14)	0.0712 (18)	0.083 (2)	0.0059 (13)	0.0242 (14)	0.0050 (15)
S3	0.0457 (3)	0.0504 (4)	0.0778 (5)	0.0068 (3)	0.0244 (3)	0.0075 (3)
S1	0.0477 (3)	0.0377 (3)	0.0634 (4)	−0.0060 (2)	0.0192 (3)	0.0043 (3)
S2	0.0418 (3)	0.0538 (4)	0.0603 (4)	−0.0103 (3)	0.0203 (3)	−0.0044 (3)
N1	0.0373 (9)	0.0368 (10)	0.0511 (11)	−0.0027 (8)	0.0179 (8)	0.0035 (8)
N2	0.0384 (10)	0.0408 (10)	0.0489 (11)	−0.0009 (8)	0.0158 (8)	0.0011 (8)
C1	0.0428 (12)	0.0364 (11)	0.0439 (12)	−0.0031 (9)	0.0155 (10)	0.0012 (9)
C2	0.0426 (12)	0.0432 (12)	0.0402 (12)	−0.0044 (10)	0.0146 (10)	−0.0048 (9)
S6	0.0477 (4)	0.0524 (4)	0.0906 (5)	0.0060 (3)	0.0264 (4)	−0.0029 (3)
S4	0.0507 (4)	0.0375 (3)	0.0862 (5)	−0.0065 (3)	0.0235 (3)	−0.0008 (3)
S5	0.0433 (3)	0.0608 (4)	0.0790 (5)	−0.0070 (3)	0.0235 (3)	0.0066 (3)
N3	0.0355 (9)	0.0385 (10)	0.0559 (12)	−0.0022 (8)	0.0134 (9)	−0.0012 (8)
N4	0.0389 (10)	0.0429 (11)	0.0586 (12)	−0.0011 (8)	0.0136 (9)	0.0008 (9)
C5	0.0422 (12)	0.0389 (12)	0.0480 (13)	−0.0049 (10)	0.0148 (10)	−0.0036 (10)
C6	0.0399 (12)	0.0467 (13)	0.0472 (13)	−0.0025 (10)	0.0129 (10)	0.0017 (10)

Geometric parameters (Å, º) top

C3—N1	1.460 (3)	C8—H8C	0.96
C3—H3A	0.96	S3—C1	1.662 (2)
C3—H3B	0.96	S1—C1	1.736 (2)
C3—H3C	0.96	S1—C2	1.737 (2)
C4—S2	1.796 (3)	S2—C2	1.735 (2)
C4—H4A	0.96	N1—C1	1.326 (3)
C4—H4B	0.96	N1—N2	1.385 (2)
C4—H4C	0.96	N2—C2	1.294 (3)
C7—N3	1.459 (3)	S6—C5	1.655 (2)
C7—H7A	0.96	S4—C6	1.735 (2)
C7—H7B	0.96	S4—C5	1.738 (2)
C7—H7C	0.96	S5—C6	1.734 (2)
C8—S5	1.797 (3)	N3—C5	1.331 (3)
C8—H8A	0.96	N3—N4	1.382 (3)
C8—H8B	0.96	N4—C6	1.289 (3)

S3···S2ⁱ	3.6438 (10)	S1···S6^v	3.3621 (10)
S2···S2ⁱⁱ	3.6319 (9)	S1···S5^iv	3.8332 (11)
S6···S5ⁱⁱⁱ	3.7189 (11)	S2···S4^v	3.8778 (10)
S3···S4^iv	3.3671 (10)

N1—C3—H3A	109.5	C1—S1—C2	89.52 (10)
N1—C3—H3B	109.5	C2—S2—C4	99.90 (11)
H3A—C3—H3B	109.5	C1—N1—N2	118.46 (17)
N1—C3—H3C	109.5	C1—N1—C3	124.32 (19)
H3A—C3—H3C	109.5	N2—N1—C3	117.18 (17)
H3B—C3—H3C	109.5	C2—N2—N1	109.28 (18)
S2—C4—H4A	109.5	N1—C1—S3	128.21 (17)
S2—C4—H4B	109.5	N1—C1—S1	108.08 (16)
H4A—C4—H4B	109.5	S3—C1—S1	123.71 (13)
S2—C4—H4C	109.5	N2—C2—S2	124.35 (18)
H4A—C4—H4C	109.5	N2—C2—S1	114.66 (17)
H4B—C4—H4C	109.5	S2—C2—S1	120.96 (13)
N3—C7—H7A	109.5	C6—S4—C5	89.64 (11)
N3—C7—H7B	109.5	C6—S5—C8	100.60 (12)
H7A—C7—H7B	109.5	C5—N3—N4	118.36 (18)
N3—C7—H7C	109.5	C5—N3—C7	123.90 (19)
H7A—C7—H7C	109.5	N4—N3—C7	117.72 (18)
H7B—C7—H7C	109.5	C6—N4—N3	109.63 (18)
S5—C8—H8A	109.5	N3—C5—S6	127.83 (17)
S5—C8—H8B	109.5	N3—C5—S4	107.77 (16)
H8A—C8—H8B	109.5	S6—C5—S4	124.40 (14)
S5—C8—H8C	109.5	N4—C6—S5	124.94 (18)
H8A—C8—H8C	109.5	N4—C6—S4	114.57 (17)
H8B—C8—H8C	109.5	S5—C6—S4	120.49 (13)

Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+1/2; (v) −x, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1,C2,N1,N2,S1 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4C···Cg1^vi	0.96	2.86	3.589 (3)	134

Symmetry code: (vi) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₄H₆N₂S₃
M_r	178.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	9.3505 (4), 22.4118 (9), 7.6682 (5)
β (°)	106.661 (5)
V (Å³)	1539.50 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.3 × 0.2 × 0.2

Data collection
Diffractometer	Oxford Diffraction Gemini CCD S Ultra
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.81, 0.84
No. of measured, independent and observed [I > 2σ(I)] reflections	32965, 3821, 2690
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.102, 1.04
No. of reflections	3821
No. of parameters	167
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.27

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected interatomic distances (Å) top

S3···S2ⁱ	3.6438 (10)	S1···S6^v	3.3621 (10)
S2···S2ⁱⁱ	3.6319 (9)	S1···S5^iv	3.8332 (11)
S6···S5ⁱⁱⁱ	3.7189 (11)	S2···S4^v	3.8778 (10)
S3···S4^iv	3.3671 (10)

Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, y−1/2, −z+1/2; (v) −x, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1,C2,N1,N2,S1 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4C···Cg1^vi	0.96	2.86	3.589 (3)	134

Symmetry code: (vi) −x, −y+1, −z.

X-π contacts (X: Cg, S). top

G1···G2	d(G1-G2)(Å)	d(G1-G1*)(Å)	<G1*-G1-G2>(°)
Cg2···Cg2^vii	3.8958 (13)	3.7320 (9)	16.27 (2)
S3···Cg1^viii	3.7271 (11)	3.5532 (13)	17.66 (2)

Symmetry codes: (vii) x,3/2-y,1/2+z; (viii) 1-x, 1-y, 1-z. Cg1 and Cg2 are the centroids of the C1,C2,N1,N2,S1 and C5,C6,N3,N4,S4 rings, respectively.

d(G1-G2): G1-G2 vector length; G1*: projection of the G1 centre onto the G2 plane. <G1*-G1-G2>: angle subtended by the G1*-G1 and G2-G1 vectors.

Table 4: Comparative table of S···S distances (Å) found in closely related structures I (this work), II (Bats, 1976) and III (Mrozek et al., 2000). top

(I)	(II)*	(III)
3.3621 (10)[-0.24]	3.565[-0.04]	3.577 (4)[-0.03]
3.3671 (10)[-0.23]	3.694[+0.09]	3.890 (4)[+0.29]
3.6319( 9)[+0.03]	3.771[+0.17]	3.906 (4)[+0.30]
3.6438 (10)[+0.04]	3.924[+0.32]	3.975 (4)[+0.37]
3.7189 (11)[+0.11]
3.8332 (11)[+0.23]
3.8778 (10)[+0.28]

*: su's not provided in the original work. In square brackets, deviations from the sum of commonly accepted Van der Waals radii (Bondi, 1964).

Acknowledgements

The authors acknowledge the University Grants Commission (UGC), Bangladesh, for the award of a fellowship to BG and thank the Third World Academy of Sciences (TWAS), Trieste, Italy, for awarding a TWAS–UNESCO Associateship to TGR. They are also grateful to the Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT) for a grant (PME–2006–01113).

References

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Volume 68| Part 10| October 2012| Pages o3045-o3046

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