Bis[2-(1,3-benzothia­zol-2-ylsulfan­yl)eth­yl] ether

Chen, H.-G.; Li, X.-F.; An, Y.; Yao, L.-H.; Liu, W.-S.

doi:10.1107/S1600536809052301

organic compounds

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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o125

doi:10.1107/S1600536809052301

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Bis[2-(1,3-benzothiazol-2-ylsulfanyl)ethyl] ether

Hui-Guo Chen,^a Xiao-Feng Li,^b Yan An,^b Li-Hui Yao ^c and Wei-Sheng Liu ^a ^*

^aKey Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, People's Republic of China, ^bInstitute of Marine Material and Engineering, Shanghai Maritime University, Shanghai 200135, People's Republic of China, and ^cCollege of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, People's Republic of China
^*Correspondence e-mail: liuws@lzu.edu.cn

(Received 10 November 2009; accepted 5 December 2009; online 12 December 2009)

The complete molecule of title compound, C₁₈H₁₆N₂OS₄, is generated by crystallographic twofold symmetry, with the O atom lying on the rotation axis. The dihedral angle between the ring systems is 80.91 (2)°. In the crystal, adjacent molecules are connected through π–π stacking interactions [centroid–centroid distance = 3.882 (2) Å], forming a three-dimensional network.

Related literature

For coordination polymers in supramolecular chemistry and crystal engineering, see: Robinson & Zaworotko (1995 ); Yaghi & Li (1996 ); Fujita et al. (1995 ); Tong et al. (2000 ); Bu et al. (2003 ); Long et al. (2004 ); Massue et al. (2007 ); Zou et al. (2004 ).

Experimental

Crystal data

C₁₈H₁₆N₂OS₄
M_r = 404.57
Monoclinic, C 2/c
a = 24.617 (3) Å
b = 4.7085 (3) Å
c = 17.7866 (15) Å
β = 116.571 (13)°
V = 1843.9 (3) Å³
Z = 4
Cu Kα radiation
μ = 4.81 mm⁻¹
T = 293 K
0.18 × 0.15 × 0.07 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) T_min = 0.765, T_max = 1.000
2930 measured reflections
1682 independent reflections
1353 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.129
S = 1.05
1682 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2005 $[Oxford Diffraction (2005). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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: OLEX2 (Dolomanov et al., 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809052301/ng2684sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052301/ng2684Isup2.hkl

checkCIF report

Comment top

Ligands containing thioether and nitrogenous heterocyclic groups are well established sources for biologically active complexes. In addition, this kind of ligands may form one- or multi-dimensional supramolecular structures via the intermolecule interactions such as hydrogen-bond or π-π stacking, attracting intense attention in the field of supramolecular chemistry and crystal engineering (Robinson et al., 1995; Yaghi et al., 1996; Fujita et al., 1995; Tong et al., 2000).

Herein, we report the synthesis and structure of the title compound, namely bis[2-(benzothiazol-2-ylthio)ethyl]ether (Fig.1). As shown in Fig.2, a two-dimensional supramolecular network was formed by hydrogen bonds (Table 2) [Symmetry codes (i): x, -y + 1, z + 1/2] and S—S bonds of 3.575 (2) Å [Symmetry codes (ii): -x + 1/2, -y + 3/2, -z + 2], and there are also weak π-π stacking interactions between the phenyl rings and the thiazolyl rings of adjacent molecules with a centroid-centroid distances of 3.882 Å along b direction.

Related literature top

For coordination polymers in supramolecular chemistry and crystal engineering, see: Robinson & Zaworotko (1995); Yaghi & Li (1996); Fujita et al. (1995); Tong et al. (2000); Bu et al. (2003); Long et al. (2004); Massue et al. (2007); Zou et al. (2004).

Experimental top

Bis(2-chloroethyl)ether (0.02 mol, 2.86 g) was added dropwise to a hot mixture solution (353 K) of 2-mercaptobenzothiazole (0.04 mol, 6.69 g), KOH (0.04 mol, 2.24 g) in ethanol (100 ml), and the mixture was further stirred at 353 K for 15 h. After cooling, the precipitate was filtered, washed with ethanol and water, and recrystallized from ethanol to obtain white powder. Yield: 56% (Bu et al., 2003; Massue et al., 2007; Long et al., 2004). ¹H NMR (CDCl₃, 400 MHz): 3.56 (t, 4H), 3.89 (t, 4H), 7.25 (m, 2H), 7.39 (m, 2H), 7.70 (d, 2H), 7.82 (t, 2H). MS (ESI) m/z(%): 405.0 (M⁺¹).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis CCD (Oxford Diffraction, 2005); data reduction: CrysAlis RED (Oxford Diffraction, 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: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity.
	Fig. 2. The three-dimensional structure by molecular packing, showing the hydrogen bonds as blue dashed lines [Symmetry codes: (i) x, -y + 1, z + 1/2], S—S bonds as green dashed lines and π-π stacking interactions as red dashed lines.

Bis[2-(1,3-benzothiazol-2-ylsulfanyl)ethyl] ether top

Crystal data top

C₁₈H₁₆N₂OS₄	F(000) = 840
M_r = 404.57	D_x = 1.457 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 1595 reflections
a = 24.617 (3) Å	θ = 2.8–68.1°
b = 4.7085 (3) Å	µ = 4.81 mm⁻¹
c = 17.7866 (15) Å	T = 293 K
β = 116.571 (13)°	Block, colourless
V = 1843.9 (3) Å³	0.18 × 0.15 × 0.07 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1682 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1353 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 16.0855 pixels mm^-1	θ_max = 68.1°, θ_min = 2.8°
ω scans	h = −29→25
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2005)	k = −5→3
T_min = 0.765, T_max = 1.000	l = −21→19
2930 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.129	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0876P)²] where P = (F_o² + 2F_c²)/3
1682 reflections	(Δ/σ)_max = 0.001
114 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₈H₁₆N₂OS₄	V = 1843.9 (3) Å³
M_r = 404.57	Z = 4
Monoclinic, C2/c	Cu Kα radiation
a = 24.617 (3) Å	µ = 4.81 mm⁻¹
b = 4.7085 (3) Å	T = 293 K
c = 17.7866 (15) Å	0.18 × 0.15 × 0.07 mm
β = 116.571 (13)°

Data collection top

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1682 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2005)	1353 reflections with I > 2σ(I)
T_min = 0.765, T_max = 1.000	R_int = 0.020
2930 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.129	H-atom parameters constrained
S = 1.05	Δρ_max = 0.27 e Å⁻³
1682 reflections	Δρ_min = −0.25 e Å⁻³
114 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
C1	0.17154 (13)	0.1689 (5)	1.11310 (16)	0.0505 (6)
C2	0.18584 (15)	−0.0249 (6)	1.17798 (17)	0.0608 (7)
H2	0.2256	−0.0860	1.2098	0.073*
C3	0.13924 (18)	−0.1235 (7)	1.1936 (2)	0.0701 (8)
H3	0.1474	−0.2568	1.2359	0.084*
C4	0.08011 (16)	−0.0269 (8)	1.1470 (2)	0.0702 (8)
H4	0.0494	−0.0954	1.1591	0.084*
C5	0.06625 (15)	0.1676 (6)	1.0837 (2)	0.0614 (7)
H5	0.0266	0.2328	1.0534	0.074*
C6	0.11236 (12)	0.2665 (6)	1.06519 (15)	0.0489 (6)
C7	0.15597 (12)	0.4948 (6)	0.99910 (14)	0.0483 (6)
C8	0.09486 (13)	0.8627 (6)	0.86818 (16)	0.0532 (6)
H8C	0.0791	0.9199	0.9070	0.064*
H8B	0.0995	1.0323	0.8406	0.064*
C9	0.05001 (13)	0.6678 (5)	0.80325 (17)	0.0552 (6)
H9A	0.0683	0.5769	0.7712	0.066*
H9B	0.0370	0.5215	0.8300	0.066*
N1	0.10483 (10)	0.4522 (5)	1.00023 (13)	0.0507 (5)
S1	0.21965 (3)	0.32443 (16)	1.07717 (4)	0.0560 (2)
S2	0.16852 (3)	0.69930 (17)	0.92661 (4)	0.0592 (3)
O1	0.0000	0.8363 (5)	0.7500	0.0501 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0535 (14)	0.0516 (13)	0.0422 (12)	−0.0026 (11)	0.0176 (11)	−0.0037 (10)
C2	0.0671 (18)	0.0625 (16)	0.0465 (14)	0.0052 (13)	0.0197 (13)	0.0058 (12)
C3	0.094 (2)	0.0659 (17)	0.0546 (16)	−0.0017 (16)	0.0364 (17)	0.0077 (13)
C4	0.081 (2)	0.076 (2)	0.0661 (18)	−0.0114 (16)	0.0442 (17)	−0.0024 (15)
C5	0.0579 (16)	0.0686 (18)	0.0606 (17)	−0.0045 (13)	0.0290 (14)	−0.0061 (13)
C6	0.0530 (15)	0.0504 (13)	0.0395 (12)	−0.0021 (11)	0.0171 (11)	−0.0063 (10)
C7	0.0454 (13)	0.0524 (13)	0.0387 (11)	−0.0023 (10)	0.0112 (10)	−0.0007 (10)
C8	0.0561 (15)	0.0484 (13)	0.0442 (13)	0.0012 (11)	0.0127 (11)	0.0024 (10)
C9	0.0528 (15)	0.0482 (13)	0.0482 (13)	0.0051 (11)	0.0078 (12)	−0.0003 (11)
N1	0.0460 (11)	0.0559 (12)	0.0427 (10)	−0.0030 (9)	0.0132 (9)	−0.0023 (9)
S1	0.0438 (4)	0.0679 (5)	0.0484 (4)	0.0033 (3)	0.0136 (3)	0.0090 (3)
S2	0.0450 (4)	0.0713 (5)	0.0519 (4)	−0.0050 (3)	0.0132 (3)	0.0131 (3)
O1	0.0485 (14)	0.0462 (13)	0.0436 (12)	0.000	0.0099 (11)	0.000

Geometric parameters (Å, º) top

C1—C2	1.387 (4)	C7—N1	1.284 (4)
C1—C6	1.396 (4)	C7—S2	1.744 (3)
C1—S1	1.739 (3)	C7—S1	1.755 (3)
C2—C3	1.376 (5)	C8—C9	1.501 (4)
C2—H2	0.9300	C8—S2	1.810 (3)
C3—C4	1.390 (5)	C8—H8C	0.9700
C3—H3	0.9300	C8—H8B	0.9700
C4—C5	1.372 (5)	C9—O1	1.414 (3)
C4—H4	0.9300	C9—H9A	0.9700
C5—C6	1.395 (4)	C9—H9B	0.9700
C5—H5	0.9300	O1—C9ⁱ	1.414 (3)
C6—N1	1.394 (4)

C2—C1—C6	122.1 (3)	N1—C7—S1	116.8 (2)
C2—C1—S1	128.4 (2)	S2—C7—S1	116.50 (15)
C6—C1—S1	109.5 (2)	C9—C8—S2	112.65 (19)
C3—C2—C1	117.7 (3)	C9—C8—H8C	109.1
C3—C2—H2	121.1	S2—C8—H8C	109.1
C1—C2—H2	121.1	C9—C8—H8B	109.1
C2—C3—C4	121.0 (3)	S2—C8—H8B	109.1
C2—C3—H3	119.5	H8C—C8—H8B	107.8
C4—C3—H3	119.5	O1—C9—C8	107.0 (2)
C5—C4—C3	121.1 (3)	O1—C9—H9A	110.3
C5—C4—H4	119.4	C8—C9—H9A	110.3
C3—C4—H4	119.4	O1—C9—H9B	110.3
C4—C5—C6	119.1 (3)	C8—C9—H9B	110.3
C4—C5—H5	120.4	H9A—C9—H9B	108.6
C6—C5—H5	120.4	C7—N1—C6	110.1 (2)
N1—C6—C5	125.7 (2)	C1—S1—C7	88.23 (13)
N1—C6—C1	115.3 (2)	C7—S2—C8	101.30 (13)
C5—C6—C1	118.9 (3)	C9—O1—C9ⁱ	111.7 (3)
N1—C7—S2	126.7 (2)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱⁱ	0.93	2.71	3.358 (3)	128

Symmetry code: (ii) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₆N₂OS₄
M_r	404.57
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	24.617 (3), 4.7085 (3), 17.7866 (15)
β (°)	116.571 (13)
V (Å³)	1843.9 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	4.81
Crystal size (mm)	0.18 × 0.15 × 0.07

Data collection
Diffractometer	Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2005)
T_min, T_max	0.765, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2930, 1682, 1353
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.129, 1.05
No. of reflections	1682
No. of parameters	114
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.25

Computer programs: CrysAlis CCD (Oxford Diffraction, 2005), CrysAlis RED (Oxford Diffraction, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Acknowledgements

The authors acknowledge the NSFC (Grant Nos. 20771048,20931003), the Project of Shanghai Municipal Education Commission (2008080, 2008068, 09YZ245, 10YZ111, 10ZZ98), the `Chen Guang' project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation (09 C G52), the Innovative Activities of University Students in Shanghai Maritime University Project (090503) and the State Key Laboratory of Pollution Control and Resource Reuse Foundation (PCRRF09001) for financial support.

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