5,5′-[Methyl­enebis(sulfanedi­yl)]bis­(1,3,4-thia­diazol-2-amine)

Meng, F.

doi:10.1107/S1600536808030122

organic compounds

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Volume 64| Part 10| October 2008| Page o2000

doi:10.1107/S1600536808030122

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5,5′-[Methylenebis(sulfanediyl)]bis(1,3,4-thiadiazol-2-amine)

Fankun Meng ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Daqing Normal University, 163712 Daqing, Heilongjiang, People's Republic of China
^*Correspondence e-mail: klsz79@163.com

(Received 23 August 2008; accepted 18 September 2008; online 24 September 2008)

In the crystal structure of the title compound, C₅H₆N₆S₄, the molecules are linked by strong N—H⋯N hydrogen bonds into a two-dimensional network and an intramolecular C—H⋯S interaction also occurs.

Related literature

For the multiple coordination environment of this ligand, see: Ma et al. (2007 ).

Experimental

Crystal data

C₅H₆N₆S₄
M_r = 278.40
Triclinic, $[P \overline 1]$
a = 5.457 (3) Å
b = 7.316 (4) Å
c = 13.623 (8) Å
α = 81.746 (8)°
β = 88.864 (8)°
γ = 74.858 (8)°
V = 519.5 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 298 (2) K
0.28 × 0.19 × 0.14 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.789, T_max = 0.886
2686 measured reflections
1801 independent reflections
1525 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.130
S = 1.00
1801 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N5ⁱ	0.86	2.18	2.999 (4)	158
N6—H6A⋯N2ⁱ	0.86	2.18	3.023 (4)	168
N6—H6B⋯N1ⁱⁱ	0.86	2.19	3.021 (4)	162
C5—H5A⋯S1	0.97	2.82	3.364 (4)	116
Symmetry codes: (i) -x+2, -y+1, -z+2; (ii) x+1, y-1, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030122/bx2173sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808030122/bx2173Isup2.hkl

checkCIF report

Comment top

5-amino-4H-pyrazole-3-thiol ligand and its derivatives are widely studied because of their multiply coordination environment (Ma, et al., 2007). They represent a class of highly useful compounds in which the presence of S and N atoms renders various hydrogen bonding motifs leading to the formation of versatile supramolecular architecture. As continuous study of this ligand we report here the structure of the title compound,(I)(Fig. 1). In the crystal structure of the title compound, the molecules are linked by strong N—H···N hydrogen bonds into a two-dimensional network, Fig 2. An intramolecular C-H···S interaction also occurs.

Related literature top

For the multiple coordination environment of this ligand, see: Ma et al. (2007).

Experimental top

5-amino-1,3,4-thiadiazole-2-thiol(2 mmol), and sodium ethanolate were dissolved in ethanol, and the mixture was stirred for 4 h at 323 K. After cooling at room temperature, the solution was filtered. The solvent was removed from the filtrate under vacuum, and the solid residue was recrystallized from diethylether; colorless crystals suitable for X-Ray diffraction study were obtained. Yield, 81%. m.p. 368 K. Analysis, calculated for C₅H₆N₆S₄: C 21.57, H 2.17, N 30.19; found: C 21.36, H 2.43, N 30.32. The elemental analyses were performed with a Perkine Elemer PE2400II instrument.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme. The H atoms are omitted for clarity.
	Fig. 2. The crystal packing of (I), viewed along the a axis. Dashed lines show intermolecular hydrogen bonds.

5,5'-[Methylenebis(sulfanediyl)]bis(1,3,4-thiadiazol-2-amine) top

Crystal data top

C₅H₆N₆S₄	Z = 2
M_r = 278.40	F(000) = 284
Triclinic, P1	D_x = 1.780 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.457 (3) Å	Cell parameters from 1816 reflections
b = 7.316 (4) Å	θ = 2.9–28.3°
c = 13.623 (8) Å	µ = 0.89 mm⁻¹
α = 81.746 (8)°	T = 298 K
β = 88.864 (8)°	Block, colourless
γ = 74.858 (8)°	0.28 × 0.19 × 0.14 mm
V = 519.5 (5) Å³

Data collection top

Siemens SMART CCD area-detector diffractometer	1801 independent reflections
Radiation source: fine-focus sealed tube	1525 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→6
T_min = 0.789, T_max = 0.886	k = −7→8
2686 measured reflections	l = −15→16

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.09P)² + 0.0868P] where P = (F_o² + 2F_c²)/3
1801 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

C₅H₆N₆S₄	γ = 74.858 (8)°
M_r = 278.40	V = 519.5 (5) Å³
Triclinic, P1	Z = 2
a = 5.457 (3) Å	Mo Kα radiation
b = 7.316 (4) Å	µ = 0.89 mm⁻¹
c = 13.623 (8) Å	T = 298 K
α = 81.746 (8)°	0.28 × 0.19 × 0.14 mm
β = 88.864 (8)°

Data collection top

Siemens SMART CCD area-detector diffractometer	1801 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1525 reflections with I > 2σ(I)
T_min = 0.789, T_max = 0.886	R_int = 0.034
2686 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.00	Δρ_max = 0.47 e Å⁻³
1801 reflections	Δρ_min = −0.65 e Å⁻³
136 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
N1	0.7436 (5)	0.9404 (4)	0.81430 (19)	0.0378 (6)
N2	0.8979 (5)	0.8670 (4)	0.89745 (18)	0.0391 (6)
N3	1.3224 (5)	0.7099 (4)	0.94128 (19)	0.0466 (7)
H3A	1.2912	0.7013	1.0037	0.056*
H3B	1.4740	0.6646	0.9216	0.056*
N4	0.7147 (5)	0.4974 (4)	0.77661 (18)	0.0393 (6)
N5	0.8645 (5)	0.3914 (4)	0.85485 (18)	0.0404 (6)
N6	1.2775 (5)	0.1997 (4)	0.89166 (18)	0.0417 (7)
H6A	1.2482	0.1837	0.9541	0.050*
H6B	1.4246	0.1472	0.8701	0.050*
S1	1.18916 (14)	0.81717 (11)	0.74813 (5)	0.0366 (3)
S2	0.72542 (15)	1.00787 (11)	0.61469 (6)	0.0398 (3)
S3	1.13900 (15)	0.34844 (11)	0.70097 (5)	0.0378 (3)
S4	0.68122 (15)	0.60763 (11)	0.57878 (5)	0.0403 (3)
C1	0.8660 (5)	0.9238 (4)	0.7323 (2)	0.0311 (6)
C2	1.1362 (6)	0.7931 (4)	0.8752 (2)	0.0336 (7)
C3	0.8273 (6)	0.4904 (4)	0.6922 (2)	0.0329 (7)
C4	1.0953 (5)	0.3057 (4)	0.8283 (2)	0.0307 (6)
C5	0.8374 (6)	0.7999 (4)	0.55130 (19)	0.0375 (7)
H5A	1.0170	0.7468	0.5668	0.045*
H5B	0.8213	0.8433	0.4805	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0323 (14)	0.0464 (15)	0.0301 (13)	−0.0032 (11)	−0.0026 (11)	−0.0024 (11)
N2	0.0327 (14)	0.0533 (15)	0.0252 (12)	−0.0018 (11)	−0.0026 (10)	−0.0018 (11)
N3	0.0344 (15)	0.0664 (18)	0.0280 (13)	0.0011 (13)	−0.0066 (11)	0.0039 (13)
N4	0.0341 (14)	0.0451 (14)	0.0297 (13)	0.0008 (11)	−0.0016 (11)	0.0037 (11)
N5	0.0353 (15)	0.0494 (15)	0.0286 (13)	−0.0012 (12)	−0.0006 (11)	0.0020 (11)
N6	0.0337 (14)	0.0516 (16)	0.0293 (13)	0.0020 (12)	−0.0038 (11)	0.0054 (12)
S1	0.0276 (4)	0.0498 (5)	0.0267 (4)	−0.0028 (3)	−0.0016 (3)	0.0002 (3)
S2	0.0398 (5)	0.0424 (5)	0.0300 (4)	−0.0032 (3)	−0.0097 (3)	0.0062 (3)
S3	0.0356 (5)	0.0438 (5)	0.0276 (4)	−0.0004 (3)	−0.0002 (3)	−0.0024 (3)
S4	0.0401 (5)	0.0507 (5)	0.0287 (4)	−0.0111 (4)	−0.0122 (3)	−0.0014 (3)
C1	0.0298 (15)	0.0323 (14)	0.0285 (14)	−0.0068 (12)	−0.0049 (12)	0.0028 (11)
C2	0.0353 (16)	0.0368 (15)	0.0264 (14)	−0.0075 (12)	−0.0040 (12)	0.0002 (12)
C3	0.0321 (15)	0.0343 (15)	0.0302 (15)	−0.0070 (12)	−0.0056 (12)	−0.0006 (12)
C4	0.0336 (16)	0.0290 (14)	0.0275 (14)	−0.0065 (12)	−0.0031 (12)	−0.0004 (11)
C5	0.0370 (17)	0.0525 (18)	0.0186 (13)	−0.0082 (14)	−0.0049 (12)	0.0032 (12)

Geometric parameters (Å, º) top

N1—C1	1.295 (4)	N6—H6B	0.8600
N1—N2	1.381 (4)	S1—C1	1.736 (3)
N2—C2	1.319 (4)	S1—C2	1.741 (3)
N3—C2	1.330 (4)	S2—C1	1.747 (3)
N3—H3A	0.8600	S2—C5	1.818 (3)
N3—H3B	0.8600	S3—C4	1.741 (3)
N4—C3	1.294 (4)	S3—C3	1.742 (3)
N4—N5	1.368 (3)	S4—C3	1.752 (3)
N5—C4	1.321 (4)	S4—C5	1.819 (3)
N6—C4	1.332 (4)	C5—H5A	0.9700
N6—H6A	0.8600	C5—H5B	0.9700

C1—N1—N2	112.9 (2)	S1—C1—S2	121.83 (17)
C2—N2—N1	112.6 (2)	N2—C2—N3	124.8 (3)
C2—N3—H3A	120.0	N2—C2—S1	113.2 (2)
C2—N3—H3B	120.0	N3—C2—S1	122.0 (2)
H3A—N3—H3B	120.0	N4—C3—S3	113.7 (2)
C3—N4—N5	113.4 (2)	N4—C3—S4	123.8 (2)
C4—N5—N4	113.0 (2)	S3—C3—S4	122.55 (17)
C4—N6—H6A	120.0	N5—C4—N6	124.1 (3)
C4—N6—H6B	120.0	N5—C4—S3	112.8 (2)
H6A—N6—H6B	120.0	N6—C4—S3	123.1 (2)
C1—S1—C2	86.94 (14)	S2—C5—S4	117.40 (16)
C1—S2—C5	101.78 (13)	S2—C5—H5A	108.0
C4—S3—C3	87.09 (13)	S4—C5—H5A	108.0
C3—S4—C5	101.31 (13)	S2—C5—H5B	108.0
N1—C1—S1	114.3 (2)	S4—C5—H5B	108.0
N1—C1—S2	123.8 (2)	H5A—C5—H5B	107.2

C1—N1—N2—C2	−1.0 (4)	N5—N4—C3—S3	−0.1 (3)
C3—N4—N5—C4	0.9 (4)	N5—N4—C3—S4	178.7 (2)
N2—N1—C1—S1	−0.7 (3)	C4—S3—C3—N4	−0.6 (2)
N2—N1—C1—S2	−178.4 (2)	C4—S3—C3—S4	−179.3 (2)
C2—S1—C1—N1	1.5 (2)	C5—S4—C3—N4	107.8 (3)
C2—S1—C1—S2	179.36 (19)	C5—S4—C3—S3	−73.5 (2)
C5—S2—C1—N1	−130.4 (3)	N4—N5—C4—N6	177.8 (3)
C5—S2—C1—S1	52.0 (2)	N4—N5—C4—S3	−1.4 (3)
N1—N2—C2—N3	−178.6 (3)	C3—S3—C4—N5	1.1 (2)
N1—N2—C2—S1	2.2 (3)	C3—S3—C4—N6	−178.1 (3)
C1—S1—C2—N2	−2.1 (2)	C1—S2—C5—S4	77.73 (18)
C1—S1—C2—N3	178.7 (3)	C3—S4—C5—S2	−79.41 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N5ⁱ	0.86	2.18	2.999 (4)	158
N6—H6A···N2ⁱ	0.86	2.18	3.023 (4)	168
N6—H6B···N1ⁱⁱ	0.86	2.19	3.021 (4)	162
C5—H5A···S1	0.97	2.82	3.364 (4)	116

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

Experimental details

Crystal data
Chemical formula	C₅H₆N₆S₄
M_r	278.40
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.457 (3), 7.316 (4), 13.623 (8)
α, β, γ (°)	81.746 (8), 88.864 (8), 74.858 (8)
V (Å³)	519.5 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.28 × 0.19 × 0.14

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.789, 0.886
No. of measured, independent and observed [I > 2σ(I)] reflections	2686, 1801, 1525
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.130, 1.00
No. of reflections	1801
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.65

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N5ⁱ	0.86	2.18	2.999 (4)	158
N6—H6A···N2ⁱ	0.86	2.18	3.023 (4)	168
N6—H6B···N1ⁱⁱ	0.86	2.19	3.021 (4)	162
C5—H5A···S1	0.97	2.82	3.364 (4)	116

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

Acknowledgements

The authors thank the Postgraduate Foundation of Taishan University (No. Y07-2-15) for financial support.

References

Ma, C. L., Sun, J. S., Zhang, R. F. & Wang, D. Q. (2007). J. Organomet. Chem. 692, 4029–4042. Web of Science CSD CrossRef CAS Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar