1,2-Bis­(benzo­thia­zol-2-yl­sulfanyl)­ethane

The title compound, C₁₆H₁₂N₂S₄, was synthesized by reaction of 1,2-di­bromo­ethane with the sodium salt of 2-mer­capto­benzo­thia­zole. The mol­ecule has an approximate inversion centre, with two benzo­thia­zole fragments having an antiparallel orientation, their least-squares planes forming a dihedral angle of 4.12 (12)°. The central four-atom S—C—C—S link is almost planar, its plane being approximately orthogonal to the benzo­thia­zole planes [dihedral angles 84.98 (14) and 84.13 (15)°]. Intermolecular S...S interactions [3.657 (3) Å] link the mol­ecules in the crystal structure into infinite chains stretching along the [10] direction.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.039
• wR factor = 0.094
• Data-to-parameter ratio = 14.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

Numerous flexible or rigid multi-thioether ligands containing N-heterocyclic entities have been synthesized and studied. They attract substantial attention due to their diverse coordination capabilities and important properties of their metal complexes (Bu et al., 2002; Hong et al., 2000; Alcock et al., 1978). In addition, studies of the S-containing compounds have also been carried out with the goal of designing an improved optical sensor for the Ag^I ion (Lerchi et al., 1996). As a continuation of our systematic studies of the coordination chemistry of various multi-thioether ligands and the architecture of their polymeric metal complexes, a dithioether ligand with `terminal' benzothiazole groups, namely 1,2-bis(benzothiazol-2-ylsulfanyl)ethane, (I), has been synthesized.

As shown in Fig. 1, the molecule of (I) has an approximate inversion centre, with two benzothiazole rings having an antiparallel orientation, the dihedral angle formed by their mean planes being 4.12 (12)°. The central four-atom S—C—C—S link is planar to within 0.01 Å and almost orthogonal to benzothiazole mean planes, the dihedral angles being 84.98 (14) and 84.13 (15)° for the S1- and S4-containing benzothiazole systems, respectively.

Intermolecular S1···S4ⁱ interactions [3.657 (3) Å; symmetry code (i): 0.5 + x, 0.5 − y, −0.5 + z] link the molecules in crystal into the infinite chains stretching along the [101] direction. In addition, π–π-stacking interactions between the benzothiazole fragments of the neighbouring molecules is observed; the average separation between the corresponding atoms is 3.895 Å.

S2. Experimental

The title compound has been synthesized by the reaction of 1,2-dibromoethane and the sodium salt of 2-mercaptobenzothiazole in EtOH at 353 K, as described by Liu et al. (2001) (yield: 80%, m.p.: 411–413 K). Yellow single crystals of the title compound were obtained by recrystallization from chloroform.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. View of the title compound, with displacement ellipsoids at the 30% probability level. H atoms have been omitted.

1,2-bis(benzothiazol-2-ylsulfanyl)ethane

Crystal data

C16H12N2S4	F(000) = 744
Mr = 360.53	Dx = 1.514 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 11.534 (4) Å	Cell parameters from 719 reflections
b = 10.719 (4) Å	θ = 3.7–25.6°
c = 14.006 (5) Å	µ = 0.60 mm^−1
β = 114.029 (5)°	T = 293 K
V = 1581.5 (10) Å^3	Needle, yellow
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2791 independent reflections
Radiation source: fine-focus sealed tube	1833 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ϕ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.841, Tmax = 0.890	k = −12→6
6363 measured reflections	l = −15→16

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0413P)^2 + 0.2548P] where P = (Fo^2 + 2Fc^2)/3
2791 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.71656 (7)	0.53816 (7)	0.11326 (6)	0.0529 (2)
S2	0.73711 (8)	0.40329 (8)	0.30512 (6)	0.0618 (3)
S3	0.43280 (8)	0.33636 (8)	0.41476 (7)	0.0626 (3)
S4	0.43831 (7)	0.19798 (8)	0.59982 (6)	0.0591 (3)
N1	0.5573 (2)	0.5757 (2)	0.19906 (17)	0.0461 (6)
N2	0.6112 (2)	0.1659 (2)	0.52809 (18)	0.0466 (6)
C1	0.5964 (2)	0.6467 (2)	0.0549 (2)	0.0415 (7)
C2	0.5719 (3)	0.7194 (3)	−0.0323 (2)	0.0533 (8)
H2	0.6217	0.7134	−0.0702	0.064*
C3	0.4708 (3)	0.8019 (3)	−0.0618 (2)	0.0645 (9)
H3	0.4523	0.8518	−0.1205	0.077*
C4	0.3975 (3)	0.8107 (3)	−0.0054 (3)	0.0639 (9)
H4	0.3305	0.8672	−0.0265	0.077*
C5	0.4210 (3)	0.7377 (3)	0.0819 (2)	0.0553 (8)
H5	0.3704	0.7443	0.1191	0.066*
C6	0.5217 (2)	0.6542 (2)	0.1129 (2)	0.0419 (7)
C7	0.6560 (3)	0.5113 (3)	0.2078 (2)	0.0449 (7)
C8	0.6432 (3)	0.4090 (3)	0.3827 (2)	0.0626 (9)
H8A	0.6954	0.3826	0.4536	0.075*
H8B	0.6169	0.4943	0.3856	0.075*
C9	0.5291 (3)	0.3279 (3)	0.3388 (2)	0.0595 (8)
H9A	0.5556	0.2422	0.3376	0.071*
H9B	0.4780	0.3529	0.2674	0.071*
C10	0.5096 (3)	0.2275 (3)	0.5127 (2)	0.0459 (7)
C11	0.6412 (3)	0.0865 (2)	0.6133 (2)	0.0425 (7)
C12	0.7435 (3)	0.0061 (3)	0.6508 (2)	0.0523 (8)
H12	0.7989	0.0009	0.6179	0.063*
C13	0.7629 (3)	−0.0663 (3)	0.7374 (2)	0.0600 (8)
H13	0.8327	−0.1193	0.7633	0.072*
C14	0.6800 (3)	−0.0611 (3)	0.7862 (2)	0.0629 (9)
H14	0.6940	−0.1113	0.8440	0.075*
C15	0.5769 (3)	0.0179 (3)	0.7498 (2)	0.0586 (8)
H15	0.5215	0.0218	0.7828	0.070*
C16	0.5575 (3)	0.0913 (3)	0.6633 (2)	0.0467 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0522 (5)	0.0555 (5)	0.0584 (5)	0.0106 (4)	0.0302 (4)	0.0053 (4)
S2	0.0555 (5)	0.0658 (6)	0.0626 (5)	0.0109 (4)	0.0225 (4)	0.0205 (4)
S3	0.0566 (5)	0.0582 (6)	0.0728 (6)	0.0083 (4)	0.0260 (5)	0.0143 (4)
S4	0.0499 (5)	0.0646 (6)	0.0737 (6)	0.0013 (4)	0.0363 (4)	0.0041 (4)
N1	0.0448 (14)	0.0468 (15)	0.0511 (14)	0.0024 (12)	0.0241 (12)	0.0053 (12)
N2	0.0469 (14)	0.0470 (15)	0.0508 (14)	0.0013 (12)	0.0250 (12)	0.0022 (12)
C1	0.0435 (16)	0.0363 (16)	0.0455 (16)	−0.0041 (13)	0.0190 (13)	−0.0055 (13)
C2	0.062 (2)	0.055 (2)	0.0506 (18)	−0.0031 (16)	0.0302 (16)	0.0036 (16)
C3	0.071 (2)	0.057 (2)	0.062 (2)	−0.0013 (18)	0.0240 (18)	0.0206 (17)
C4	0.055 (2)	0.051 (2)	0.084 (2)	0.0108 (16)	0.0258 (19)	0.0147 (18)
C5	0.0495 (19)	0.0479 (19)	0.077 (2)	0.0048 (15)	0.0342 (18)	0.0042 (17)
C6	0.0412 (16)	0.0364 (16)	0.0483 (17)	−0.0055 (13)	0.0183 (14)	−0.0007 (13)
C7	0.0445 (17)	0.0435 (17)	0.0470 (17)	−0.0034 (14)	0.0191 (14)	0.0010 (13)
C8	0.071 (2)	0.062 (2)	0.0474 (18)	−0.0081 (18)	0.0162 (17)	0.0064 (16)
C9	0.067 (2)	0.055 (2)	0.0495 (18)	−0.0037 (16)	0.0159 (16)	0.0057 (15)
C10	0.0437 (17)	0.0446 (17)	0.0508 (17)	−0.0091 (14)	0.0207 (14)	−0.0051 (14)
C11	0.0434 (16)	0.0392 (16)	0.0454 (16)	−0.0082 (13)	0.0185 (14)	−0.0027 (14)
C12	0.0577 (19)	0.0518 (19)	0.0544 (19)	0.0016 (16)	0.0299 (16)	0.0003 (15)
C13	0.062 (2)	0.052 (2)	0.060 (2)	0.0047 (16)	0.0188 (17)	0.0059 (17)
C14	0.072 (2)	0.063 (2)	0.0506 (19)	−0.0170 (19)	0.0214 (18)	0.0040 (17)
C15	0.064 (2)	0.063 (2)	0.056 (2)	−0.0191 (18)	0.0329 (18)	−0.0065 (17)
C16	0.0470 (17)	0.0461 (18)	0.0518 (17)	−0.0112 (14)	0.0251 (15)	−0.0053 (14)

Geometric parameters (Å, º)

S1—C1	1.738 (3)	C4—H4	0.93
S1—C7	1.754 (3)	C5—C6	1.388 (4)
S2—C7	1.742 (3)	C5—H5	0.93
S2—C8	1.821 (3)	C8—C9	1.486 (4)
S3—C9	1.827 (3)	C8—H8A	0.97
S3—C10	1.743 (3)	C8—H8B	0.97
S4—C10	1.755 (3)	C9—H9A	0.97
S4—C16	1.730 (3)	C9—H9B	0.97
N1—C6	1.390 (3)	C11—C12	1.380 (4)
N1—C7	1.294 (3)	C11—C16	1.406 (4)
N2—C10	1.284 (3)	C12—C13	1.379 (4)
N2—C11	1.391 (3)	C12—H12	0.93
C1—C2	1.378 (4)	C13—C14	1.385 (4)
C1—C6	1.406 (3)	C13—H13	0.93
C2—C3	1.385 (4)	C14—C15	1.377 (4)
C2—H2	0.93	C14—H14	0.93
C3—C4	1.376 (4)	C15—C16	1.384 (4)
C3—H3	0.93	C15—H15	0.93
C4—C5	1.383 (4)
C1—S1—C7	88.77 (13)	C9—C8—H8B	109.2
C7—S2—C8	100.64 (14)	S2—C8—H8B	109.2
C10—S3—C9	100.98 (14)	H8A—C8—H8B	107.9
C16—S4—C10	88.73 (13)	C8—C9—S3	112.1 (2)
C7—N1—C6	110.0 (2)	C8—C9—H9A	109.2
C10—N2—C11	110.5 (2)	S3—C9—H9A	109.2
C2—C1—C6	121.7 (3)	C8—C9—H9B	109.2
C2—C1—S1	129.2 (2)	S3—C9—H9B	109.2
C6—C1—S1	109.0 (2)	H9A—C9—H9B	107.9
C1—C2—C3	118.0 (3)	N2—C10—S3	127.8 (2)
C1—C2—H2	121.0	N2—C10—S4	116.4 (2)
C3—C2—H2	121.0	S3—C10—S4	115.86 (17)
C4—C3—C2	120.8 (3)	C12—C11—N2	125.8 (2)
C4—C3—H3	119.6	C12—C11—C16	119.2 (3)
C2—C3—H3	119.6	N2—C11—C16	115.0 (2)
C3—C4—C5	121.6 (3)	C13—C12—C11	119.6 (3)
C3—C4—H4	119.2	C13—C12—H12	120.2
C5—C4—H4	119.2	C11—C12—H12	120.2
C4—C5—C6	118.7 (3)	C12—C13—C14	120.9 (3)
C4—C5—H5	120.7	C12—C13—H13	119.5
C6—C5—H5	120.7	C14—C13—H13	119.5
C5—C6—N1	125.2 (2)	C15—C14—C13	120.5 (3)
C5—C6—C1	119.2 (3)	C15—C14—H14	119.7
N1—C6—C1	115.6 (2)	C13—C14—H14	119.7
N1—C7—S2	126.9 (2)	C14—C15—C16	118.8 (3)
N1—C7—S1	116.5 (2)	C14—C15—H15	120.6
S2—C7—S1	116.60 (16)	C16—C15—H15	120.6
C9—C8—S2	112.0 (2)	C15—C16—C11	121.0 (3)
C9—C8—H8A	109.2	C15—C16—S4	129.6 (2)
S2—C8—H8A	109.2	C11—C16—S4	109.3 (2)
C7—S1—C1—C2	179.5 (3)	C10—S3—C9—C8	−84.6 (2)
C7—S1—C1—C6	0.7 (2)	C11—N2—C10—S3	−179.0 (2)
C6—C1—C2—C3	0.3 (4)	C11—N2—C10—S4	0.4 (3)
S1—C1—C2—C3	−178.4 (2)	C9—S3—C10—N2	3.9 (3)
C1—C2—C3—C4	0.1 (5)	C9—S3—C10—S4	−175.54 (16)
C2—C3—C4—C5	−0.5 (5)	C16—S4—C10—N2	−0.2 (2)
C3—C4—C5—C6	0.4 (5)	C16—S4—C10—S3	179.31 (17)
C4—C5—C6—N1	179.5 (3)	C10—N2—C11—C12	179.3 (3)
C4—C5—C6—C1	0.0 (4)	C10—N2—C11—C16	−0.6 (3)
C7—N1—C6—C5	−178.8 (3)	N2—C11—C12—C13	179.0 (3)
C7—N1—C6—C1	0.7 (3)	C16—C11—C12—C13	−1.1 (4)
C2—C1—C6—C5	−0.3 (4)	C11—C12—C13—C14	1.1 (5)
S1—C1—C6—C5	178.6 (2)	C12—C13—C14—C15	−0.8 (5)
C2—C1—C6—N1	−179.9 (2)	C13—C14—C15—C16	0.4 (5)
S1—C1—C6—N1	−1.0 (3)	C14—C15—C16—C11	−0.3 (4)
C6—N1—C7—S2	178.4 (2)	C14—C15—C16—S4	179.9 (2)
C6—N1—C7—S1	−0.1 (3)	C12—C11—C16—C15	0.7 (4)
C8—S2—C7—N1	0.7 (3)	N2—C11—C16—C15	−179.4 (2)
C8—S2—C7—S1	179.25 (16)	C12—C11—C16—S4	−179.5 (2)
C1—S1—C7—N1	−0.4 (2)	N2—C11—C16—S4	0.4 (3)
C1—S1—C7—S2	−179.05 (17)	C10—S4—C16—C15	179.7 (3)
C7—S2—C8—C9	83.2 (2)	C10—S4—C16—C11	−0.1 (2)
S2—C8—C9—S3	−178.60 (15)