3-Methyl-5-methyl-sulfanyl-1,3,4-thia-diazole-2(3H)-thione.

The title compound, C(4)H(6)N(2)S(3), has two very similar mol-ecules per asymmetric unit. The nine non-H atoms in each mol-ecule are coplanar, both having comparable r.m.s. deviations of 0.002 Å. The main inter-est in the rather simple structure resides in a survey of very weak (in some cases, borderline) non-bonding inter-actions 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 mol-ecules 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 = 178.30

Monoclinic,

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 ▶) 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[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.102

S = 1.04

3821 reflections

167 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); 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) ▶.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812040147/zl2506sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812040147/zl2506Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812040147/zl2506Isup3.cml

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

C4H6N2S3	F(000) = 736
Mr = 178.30	Dx = 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

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

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(Fo2) + (0.0398P)2 + 0.5703P] where P = (Fo2 + 2Fc2)/3
3821 reflections	(Δ/σ)max = 0.001
167 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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
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)

	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)

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···S6v	3.3621 (10)
S2···S2ii	3.6319 (9)	S1···S5iv	3.8332 (11)
S6···S5iii	3.7189 (11)	S2···S4v	3.8778 (10)
S3···S4iv	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)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4C···Cg1vi	0.96	2.86	3.589 (3)	134

G1···G2	d(G1-G2)(Å)	d(G1-G1*)(Å)	<G1*-G1-G2>(°)
Cg2···Cg2vii	3.8958 (13)	3.7320 (9)	16.27 (2)
S3···Cg1viii	3.7271 (11)	3.5532 (13)	17.66 (2)

(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]

Table 1

Selected interatomic distances (Å)

S3⋯S2i	3.6438 (10)
S2⋯S2ii	3.6319 (9)
S6⋯S5iii	3.7189 (11)
S3⋯S4iv	3.3671 (10)
S1⋯S6v	3.3621 (10)
S1⋯S5iv	3.8332 (11)
S2⋯S4v	3.8778 (10)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

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⋯Cg1vi	0.96	2.86	3.589 (3)	134

Symmetry code: (vi) .