Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803004264/ya6152sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803004264/ya6152Isup2.hkl |
CCDC reference: 209908
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.
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.
Fig. 1. View of the title compound, with displacement ellipsoids at the 30% probability level. H atoms have been omitted. |
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) Å3 | Needle, yellow |
Z = 4 | 0.30 × 0.25 × 0.20 mm |
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 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0413P)2 + 0.2548P] where P = (Fo2 + 2Fc2)/3 |
2791 reflections | (Δ/σ)max < 0.001 |
199 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C16H12N2S4 | V = 1581.5 (10) Å3 |
Mr = 360.53 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.534 (4) Å | µ = 0.60 mm−1 |
b = 10.719 (4) Å | T = 293 K |
c = 14.006 (5) Å | 0.30 × 0.25 × 0.20 mm |
β = 114.029 (5)° |
Bruker SMART CCD area-detector diffractometer | 2791 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1833 reflections with I > 2σ(I) |
Tmin = 0.841, Tmax = 0.890 | Rint = 0.037 |
6363 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.27 e Å−3 |
2791 reflections | Δρmin = −0.21 e Å−3 |
199 parameters |
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 | ||
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) |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
Experimental details
Crystal data | |
Chemical formula | C16H12N2S4 |
Mr | 360.53 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.534 (4), 10.719 (4), 14.006 (5) |
β (°) | 114.029 (5) |
V (Å3) | 1581.5 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.60 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.841, 0.890 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6363, 2791, 1833 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.094, 1.00 |
No. of reflections | 2791 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.21 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
S1—C1 | 1.738 (3) | S4—C10 | 1.755 (3) |
S1—C7 | 1.754 (3) | S4—C16 | 1.730 (3) |
S2—C7 | 1.742 (3) | N1—C6 | 1.390 (3) |
S2—C8 | 1.821 (3) | N1—C7 | 1.294 (3) |
S3—C9 | 1.827 (3) | N2—C10 | 1.284 (3) |
S3—C10 | 1.743 (3) | N2—C11 | 1.391 (3) |
C7—S2—C8 | 100.64 (14) | C10—S3—C9 | 100.98 (14) |
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 AgI 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.