2,5-Bis[(3-chloro­benz­yl)sulfan­yl]-1,3,4-thia­diazole

Sun, N.-B.; Jin, J.-Z.; Ke, W.

doi:10.1107/S1600536812019150

organic compounds

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Volume 68| Part 6| June 2012| Page o1620

doi:10.1107/S1600536812019150

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2,5-Bis[(3-chlorobenzyl)sulfanyl]-1,3,4-thiadiazole

Na-Bo Sun,^a ^* Jian-Zhong Jin ^a and Wei Ke ^a

^aCollege of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou 310015, People's Republic of China
^*Correspondence e-mail: nabosun@gmail.com

(Received 25 April 2012; accepted 28 April 2012; online 5 May 2012)

The complete molecule of the title compound, C₁₆H₁₂Cl₂N₂S₃, is generated by crystallographic twofold symmetry, with the S atom of the thiadiazole ring lying on the rotation axis. The dihedral angle between the mean planes of the 1,3,4-thiadiazole and benzene rings is 87.19 (7)°. In the crystal, molecules are linked by C—H⋯N interactions and short S⋯S contacts [3.3389 (9) Å] occur.

Related literature

For details of the synthesis, see: Liu et al. (2012 ); Tan et al. (2012 ). For a related structure, see: Liu & Liu (2011 . For the biological activity of related compounds, see: Liu et al. (2011a ,b ).

Experimental

Crystal data

C₁₆H₁₂Cl₂N₂S₃
M_r = 399.36
Monoclinic, C 2/c
a = 17.200 (3) Å
b = 5.6604 (11) Å
c = 17.524 (4) Å
β = 92.56 (3)°
V = 1704.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 113 K
0.12 × 0.10 × 0.06 mm

Data collection

Rigaku Saturn CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.916, T_max = 0.957
5343 measured reflections
1491 independent reflections
1382 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.063
S = 1.17
1491 reflections
105 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N1ⁱ	0.93	2.59	3.514 (2)	172
Symmetry code: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear (Rigaku/MSC, 2005); 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 global, I. DOI: 10.1107/S1600536812019150/hb6758sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812019150/hb6758Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812019150/hb6758Isup3.cml

checkCIF report

Related literature top

For details of the synthesis, see: Liu et al. (2012), Tan et al. (2012). For a related structure, see: Liu & Liu (2011. For the biological activity of related compounds, see: Liu et al. (2011a,b).

Experimental top

To a stirred solution of 1,3,4-thiadiazole-2,5-dithiol (5.1 mmol) and potassium carbonate (5.6 mmol) in DMF (15 ml), 1-chloro-3-(chloromethyl)benzene (5.6 mmol) was added dropwise. The resulting mixture was stirred at room temperature overnight. The mixture was poured into water, the precipitate formed was filtered off and recrystallized from acetone to give title compound in good yields. Compound was dissolved in hot alcohol and the resulting solution was allowed to stand in air at room temperature to colourless blocks of the title compound.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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 molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level.

2,5-Bis[(3-chlorobenzyl)sulfanyl]-1,3,4-thiadiazole top

Crystal data top

C₁₆H₁₂Cl₂N₂S₃	F(000) = 816
M_r = 399.36	D_x = 1.556 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.200 (3) Å	Cell parameters from 2634 reflections
b = 5.6604 (11) Å	θ = 3.3–27.9°
c = 17.524 (4) Å	µ = 0.75 mm⁻¹
β = 92.56 (3)°	T = 113 K
V = 1704.4 (6) Å³	Block, colorless
Z = 4	0.12 × 0.10 × 0.06 mm

Data collection top

Rigaku Saturn CCD diffractometer	1491 independent reflections
Radiation source: rotating anode	1382 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.028
ω scans	θ_max = 25.0°, θ_min = 3.3°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −20→20
T_min = 0.916, T_max = 0.957	k = −6→6
5343 measured reflections	l = −14→20

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.063	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0254P)² + 1.1171P] where P = (F_o² + 2F_c²)/3
1491 reflections	(Δ/σ)_max = 0.001
105 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₆H₁₂Cl₂N₂S₃	V = 1704.4 (6) Å³
M_r = 399.36	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.200 (3) Å	µ = 0.75 mm⁻¹
b = 5.6604 (11) Å	T = 113 K
c = 17.524 (4) Å	0.12 × 0.10 × 0.06 mm
β = 92.56 (3)°

Data collection top

Rigaku Saturn CCD diffractometer	1491 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1382 reflections with I > 2σ(I)
T_min = 0.916, T_max = 0.957	R_int = 0.028
5343 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.063	H-atom parameters constrained
S = 1.17	Δρ_max = 0.25 e Å⁻³
1491 reflections	Δρ_min = −0.22 e Å⁻³
105 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	0.03445 (2)	−0.05340 (7)	0.41412 (2)	0.01769 (13)
S2	0.0000	0.13382 (10)	0.2500	0.01979 (16)
Cl1	0.36343 (2)	−0.14225 (8)	0.42335 (3)	0.03039 (14)
N1	0.01164 (7)	−0.3031 (2)	0.28829 (7)	0.0161 (3)
C1	0.22023 (9)	0.0583 (3)	0.41728 (9)	0.0198 (3)
H1	0.2061	−0.0599	0.4508	0.024*
C2	0.29495 (9)	0.0682 (3)	0.39189 (9)	0.0206 (4)
C3	0.31795 (9)	0.2422 (3)	0.34242 (9)	0.0255 (4)
H3	0.3687	0.2464	0.3263	0.031*
C4	0.26429 (10)	0.4097 (3)	0.31736 (10)	0.0284 (4)
H4	0.2789	0.5278	0.2840	0.034*
C5	0.18844 (10)	0.4023 (3)	0.34188 (9)	0.0232 (4)
H5	0.1525	0.5150	0.3245	0.028*
C6	0.16605 (9)	0.2277 (3)	0.39205 (8)	0.0171 (3)
C7	0.08449 (9)	0.2289 (3)	0.42062 (9)	0.0190 (3)
H7A	0.0540	0.3448	0.3916	0.023*
H7B	0.0869	0.2793	0.4736	0.023*
C8	0.01873 (8)	−0.0905 (3)	0.31589 (8)	0.0136 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0171 (2)	0.0229 (2)	0.0129 (2)	−0.00199 (16)	−0.00114 (15)	0.00075 (15)
S2	0.0314 (3)	0.0127 (3)	0.0149 (3)	0.000	−0.0042 (2)	0.000
Cl1	0.0197 (2)	0.0303 (3)	0.0404 (3)	0.00735 (18)	−0.00680 (18)	0.00062 (19)
N1	0.0158 (6)	0.0171 (7)	0.0153 (6)	−0.0004 (6)	0.0002 (5)	0.0007 (5)
C1	0.0191 (8)	0.0213 (8)	0.0187 (8)	−0.0008 (7)	−0.0024 (6)	−0.0009 (7)
C2	0.0169 (8)	0.0213 (8)	0.0230 (8)	0.0029 (7)	−0.0063 (6)	−0.0050 (7)
C3	0.0143 (8)	0.0314 (10)	0.0308 (9)	−0.0037 (7)	0.0006 (7)	−0.0027 (8)
C4	0.0230 (10)	0.0274 (10)	0.0348 (10)	−0.0044 (8)	0.0018 (7)	0.0074 (8)
C5	0.0198 (9)	0.0204 (9)	0.0289 (9)	0.0020 (7)	−0.0031 (7)	0.0004 (7)
C6	0.0153 (8)	0.0201 (8)	0.0156 (7)	−0.0020 (7)	−0.0030 (6)	−0.0070 (6)
C7	0.0166 (8)	0.0214 (8)	0.0190 (8)	−0.0002 (7)	−0.0009 (6)	−0.0061 (7)
C8	0.0096 (7)	0.0164 (8)	0.0149 (8)	0.0001 (6)	0.0006 (6)	0.0018 (6)

Geometric parameters (Å, º) top

S1—C8	1.7432 (15)	C2—C3	1.382 (2)
S1—C7	1.8161 (17)	C3—C4	1.381 (2)
S2—C8ⁱ	1.7367 (15)	C3—H3	0.9300
S2—C8	1.7368 (15)	C4—C5	1.392 (2)
Cl1—C2	1.7471 (17)	C4—H4	0.9300
N1—C8	1.301 (2)	C5—C6	1.389 (2)
N1—N1ⁱ	1.383 (2)	C5—H5	0.9300
C1—C2	1.380 (2)	C6—C7	1.511 (2)
C1—C6	1.395 (2)	C7—H7A	0.9700
C1—H1	0.9300	C7—H7B	0.9700

C8—S1—C7	102.72 (7)	C6—C5—C4	120.47 (16)
C8ⁱ—S2—C8	86.03 (10)	C6—C5—H5	119.8
C8—N1—N1ⁱ	112.28 (8)	C4—C5—H5	119.8
C2—C1—C6	119.25 (15)	C5—C6—C1	119.31 (15)
C2—C1—H1	120.4	C5—C6—C7	119.64 (15)
C6—C1—H1	120.4	C1—C6—C7	121.02 (14)
C1—C2—C3	121.89 (15)	C6—C7—S1	114.82 (11)
C1—C2—Cl1	119.68 (13)	C6—C7—H7A	108.6
C3—C2—Cl1	118.43 (13)	S1—C7—H7A	108.6
C4—C3—C2	118.87 (15)	C6—C7—H7B	108.6
C4—C3—H3	120.6	S1—C7—H7B	108.6
C2—C3—H3	120.6	H7A—C7—H7B	107.5
C3—C4—C5	120.22 (16)	N1—C8—S2	114.69 (11)
C3—C4—H4	119.9	N1—C8—S1	119.12 (11)
C5—C4—H4	119.9	S2—C8—S1	125.76 (9)

C6—C1—C2—C3	0.4 (2)	C5—C6—C7—S1	131.52 (14)
C6—C1—C2—Cl1	179.77 (12)	C1—C6—C7—S1	−50.67 (18)
C1—C2—C3—C4	−0.5 (3)	C8—S1—C7—C6	−69.17 (13)
Cl1—C2—C3—C4	−179.85 (13)	N1ⁱ—N1—C8—S2	−1.62 (19)
C2—C3—C4—C5	0.1 (3)	N1ⁱ—N1—C8—S1	171.24 (12)
C3—C4—C5—C6	0.4 (3)	C8ⁱ—S2—C8—N1	0.62 (7)
C4—C5—C6—C1	−0.5 (2)	C8ⁱ—S2—C8—S1	−171.70 (14)
C4—C5—C6—C7	177.37 (15)	C7—S1—C8—N1	154.09 (12)
C2—C1—C6—C5	0.1 (2)	C7—S1—C8—S2	−33.91 (11)
C2—C1—C6—C7	−177.73 (14)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱⁱ	0.93	2.59	3.514 (2)	172

Symmetry code: (ii) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂Cl₂N₂S₃
M_r	399.36
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	113
a, b, c (Å)	17.200 (3), 5.6604 (11), 17.524 (4)
β (°)	92.56 (3)
V (Å³)	1704.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.12 × 0.10 × 0.06

Data collection
Diffractometer	Rigaku Saturn CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.916, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	5343, 1491, 1382
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.063, 1.17
No. of reflections	1491
No. of parameters	105
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.22

Computer programs: CrystalClear (Rigaku/MSC, 2005), 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
C3—H3···N1ⁱ	0.93	2.59	3.514 (2)	172

Symmetry code: (i) x+1/2, y+1/2, z.

Acknowledgements

The project was supported by the Program of the Education Department of Zhejiang Province, China (Y200803060).

References

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