Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100017431/de1157sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100017431/de1157Isup2.hkl |
CCDC reference: 160003
For related literature, see: Downard et al. (1995); Duan & Rees (1997); Duan et al. (1996); Duan, Duan, Rees & Yue (1997); Honey & Steel (1991); Mellini & Merlino (1976); Phillips & Steel (1995); Richardson & Steel (2000a, 2000b, 2000c); Steel (1996a, 1996b); Weinstock et al. (1967).
The title compound was prepared from 1,4-bis(2-pyridyl)buta-1,3-diyne by reaction with trithiazyl trichloride. Full details will be described elsewhere. Crystals were obtained by slow evaporation of an ethanol solution.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.
C14H8N6S2 | Z = 2 |
Mr = 324.38 | F(000) = 332 |
Triclinic, P1 | Dx = 1.580 Mg m−3 |
a = 6.330 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.007 (7) Å | Cell parameters from 2500 reflections |
c = 12.25 (1) Å | θ = 2.8–26.3° |
α = 84.427 (9)° | µ = 0.40 mm−1 |
β = 85.113 (9)° | T = 163 K |
γ = 79.425 (9)° | Fragment, colourless |
V = 681.6 (9) Å3 | 0.46 × 0.34 × 0.10 mm |
CCD area detector diffractometer | 2772 independent reflections |
Radiation source: fine-focus sealed tube | 2016 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.039 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.5°, θmin = 2.3° |
ϕ and ω scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | k = −11→11 |
Tmin = 0.827, Tmax = 1.000 | l = −15→15 |
8929 measured reflections |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0549P)2] where P = (Fo2 + 2Fc2)/3 |
2772 reflections | (Δ/σ)max = 0.001 |
199 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C14H8N6S2 | γ = 79.425 (9)° |
Mr = 324.38 | V = 681.6 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.330 (5) Å | Mo Kα radiation |
b = 9.007 (7) Å | µ = 0.40 mm−1 |
c = 12.25 (1) Å | T = 163 K |
α = 84.427 (9)° | 0.46 × 0.34 × 0.10 mm |
β = 85.113 (9)° |
CCD area detector diffractometer | 2772 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 2016 reflections with I > 2σ(I) |
Tmin = 0.827, Tmax = 1.000 | Rint = 0.039 |
8929 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.31 e Å−3 |
2772 reflections | Δρmin = −0.28 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 | 1.02092 (10) | 1.47534 (6) | 0.65833 (4) | 0.02750 (17) | |
N2 | 1.1480 (3) | 1.4958 (2) | 0.76517 (14) | 0.0262 (4) | |
C3 | 1.2951 (4) | 1.5803 (2) | 0.73078 (16) | 0.0221 (5) | |
C4 | 1.2979 (3) | 1.6236 (2) | 0.61533 (16) | 0.0215 (5) | |
N5 | 1.1510 (3) | 1.57081 (19) | 0.56533 (14) | 0.0250 (4) | |
S1' | 1.71557 (10) | 1.59798 (7) | 0.93400 (5) | 0.03302 (19) | |
N2' | 1.6058 (3) | 1.5220 (2) | 0.84172 (14) | 0.0277 (5) | |
C3' | 1.4317 (4) | 1.6197 (2) | 0.81288 (16) | 0.0227 (5) | |
C4' | 1.3944 (4) | 1.7562 (2) | 0.86977 (17) | 0.0240 (5) | |
N5' | 1.5441 (3) | 1.7557 (2) | 0.94043 (14) | 0.0296 (5) | |
N1" | 1.5872 (3) | 1.7645 (2) | 0.60468 (14) | 0.0268 (4) | |
C2" | 1.4435 (4) | 1.7140 (2) | 0.54934 (17) | 0.0233 (5) | |
C3" | 1.4289 (4) | 1.7409 (2) | 0.43606 (17) | 0.0290 (5) | |
H3" | 1.3232 | 1.7044 | 0.4006 | 0.035* | |
C4" | 1.5715 (4) | 1.8219 (3) | 0.37657 (19) | 0.0350 (6) | |
H4" | 1.5665 | 1.8418 | 0.2992 | 0.042* | |
C5" | 1.7224 (4) | 1.8737 (3) | 0.43202 (19) | 0.0328 (6) | |
H5" | 1.8226 | 1.9297 | 0.3932 | 0.039* | |
C6" | 1.7244 (4) | 1.8425 (2) | 0.54456 (19) | 0.0313 (6) | |
H6" | 1.8288 | 1.8782 | 0.5816 | 0.038* | |
N1"' | 1.0419 (3) | 1.8628 (2) | 0.80906 (15) | 0.0279 (4) | |
C2"' | 1.2170 (4) | 1.8873 (2) | 0.85649 (16) | 0.0248 (5) | |
C3"' | 1.2279 (4) | 2.0274 (2) | 0.89459 (17) | 0.0281 (5) | |
H3"' | 1.3522 | 2.0413 | 0.9279 | 0.034* | |
C4"' | 1.0552 (4) | 2.1448 (3) | 0.88290 (17) | 0.0317 (6) | |
H4"' | 1.0610 | 2.2411 | 0.9069 | 0.038* | |
C5"' | 0.8734 (4) | 2.1217 (3) | 0.83603 (18) | 0.0318 (6) | |
H5"' | 0.7518 | 2.2003 | 0.8282 | 0.038* | |
C6"' | 0.8753 (4) | 1.9786 (3) | 0.80072 (17) | 0.0311 (6) | |
H6"' | 0.7509 | 1.9621 | 0.7688 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0316 (4) | 0.0315 (3) | 0.0229 (3) | −0.0141 (3) | −0.0007 (2) | −0.0040 (2) |
N2 | 0.0324 (12) | 0.0269 (10) | 0.0217 (10) | −0.0116 (9) | 0.0006 (8) | −0.0045 (8) |
C3 | 0.0258 (13) | 0.0195 (11) | 0.0214 (11) | −0.0053 (9) | 0.0020 (9) | −0.0044 (8) |
C4 | 0.0226 (12) | 0.0206 (11) | 0.0216 (11) | −0.0035 (9) | −0.0008 (9) | −0.0039 (8) |
N5 | 0.0277 (11) | 0.0277 (10) | 0.0210 (10) | −0.0082 (8) | −0.0013 (8) | −0.0035 (8) |
S1' | 0.0294 (4) | 0.0440 (4) | 0.0273 (3) | −0.0078 (3) | −0.0050 (3) | −0.0062 (3) |
N2' | 0.0295 (12) | 0.0337 (11) | 0.0216 (10) | −0.0103 (9) | 0.0000 (8) | −0.0033 (8) |
C3' | 0.0276 (13) | 0.0266 (12) | 0.0153 (11) | −0.0116 (10) | 0.0033 (9) | 0.0003 (9) |
C4' | 0.0277 (13) | 0.0294 (12) | 0.0173 (11) | −0.0139 (10) | 0.0022 (9) | −0.0011 (9) |
N5' | 0.0310 (12) | 0.0399 (12) | 0.0226 (10) | −0.0167 (9) | −0.0008 (8) | −0.0063 (8) |
N1" | 0.0271 (11) | 0.0289 (10) | 0.0257 (10) | −0.0088 (9) | 0.0000 (8) | −0.0036 (8) |
C2" | 0.0263 (13) | 0.0218 (11) | 0.0215 (11) | −0.0050 (9) | 0.0027 (9) | −0.0022 (9) |
C3" | 0.0297 (14) | 0.0335 (13) | 0.0247 (12) | −0.0088 (11) | −0.0017 (10) | −0.0009 (10) |
C4" | 0.0350 (15) | 0.0395 (14) | 0.0254 (13) | −0.0013 (12) | 0.0050 (11) | 0.0060 (10) |
C5" | 0.0290 (14) | 0.0304 (13) | 0.0366 (14) | −0.0070 (11) | 0.0109 (11) | 0.0014 (10) |
C6" | 0.0284 (14) | 0.0297 (13) | 0.0379 (14) | −0.0106 (11) | 0.0005 (11) | −0.0049 (10) |
N1"' | 0.0302 (12) | 0.0299 (10) | 0.0258 (10) | −0.0089 (9) | −0.0024 (8) | −0.0058 (8) |
C2"' | 0.0317 (14) | 0.0284 (12) | 0.0160 (11) | −0.0120 (10) | 0.0038 (9) | −0.0028 (9) |
C3"' | 0.0386 (15) | 0.0303 (12) | 0.0195 (12) | −0.0172 (11) | −0.0007 (10) | −0.0027 (9) |
C4"' | 0.0486 (17) | 0.0258 (12) | 0.0222 (12) | −0.0120 (12) | 0.0014 (11) | −0.0025 (9) |
C5"' | 0.0415 (16) | 0.0285 (13) | 0.0230 (12) | −0.0027 (11) | 0.0019 (11) | 0.0000 (9) |
C6"' | 0.0316 (15) | 0.0366 (14) | 0.0262 (13) | −0.0086 (11) | −0.0020 (10) | −0.0021 (10) |
S1—N5 | 1.6202 (19) | N1"—C6" | 1.343 (3) |
S1—N2 | 1.635 (2) | N1"—C2" | 1.346 (3) |
N2—C3 | 1.325 (3) | C2"—C3" | 1.393 (3) |
C3—C4 | 1.430 (3) | C3"—C4" | 1.380 (3) |
C3—C3' | 1.488 (3) | C4"—C5" | 1.388 (3) |
C4—N5 | 1.334 (3) | C5"—C6" | 1.381 (3) |
C4—C2" | 1.479 (3) | N1"'—C6"' | 1.343 (3) |
S1'—N5' | 1.626 (2) | N1"'—C2"' | 1.356 (3) |
S1'—N2' | 1.639 (2) | C2"'—C3"' | 1.402 (3) |
N2'—C3' | 1.328 (3) | C3"'—C4"' | 1.381 (3) |
C3'—C4' | 1.444 (3) | C4"'—C5"' | 1.386 (3) |
C4'—N5' | 1.336 (3) | C5"'—C6"' | 1.396 (3) |
C4'—C2"' | 1.479 (3) | ||
N5—S1—N2 | 98.96 (11) | C4'—N5'—S1' | 108.04 (15) |
C3—N2—S1 | 107.35 (15) | C6"—N1"—C2" | 116.51 (19) |
N2—C3—C4 | 113.15 (19) | N1"—C2"—C3" | 123.70 (19) |
N2—C3—C3' | 118.53 (18) | N1"—C2"—C4 | 116.31 (19) |
C4—C3—C3' | 128.32 (18) | C3"—C2"—C4 | 120.0 (2) |
N5—C4—C3 | 113.15 (18) | C4"—C3"—C2" | 118.5 (2) |
N5—C4—C2" | 119.22 (19) | C3"—C4"—C5" | 118.7 (2) |
C3—C4—C2" | 127.62 (19) | C6"—C5"—C4" | 118.9 (2) |
C4—N5—S1 | 107.39 (15) | N1"—C6"—C5" | 123.7 (2) |
N5'—S1'—N2' | 98.92 (11) | C6"'—N1"'—C2"' | 117.3 (2) |
C3'—N2'—S1' | 107.18 (16) | N1"'—C2"'—C3"' | 122.2 (2) |
N2'—C3'—C4' | 113.6 (2) | N1"'—C2"'—C4' | 116.37 (19) |
N2'—C3'—C3 | 119.54 (19) | C3"'—C2"'—C4' | 121.4 (2) |
C4'—C3'—C3 | 126.8 (2) | C4"'—C3"'—C2"' | 119.0 (2) |
N5'—C4'—C3' | 112.2 (2) | C3"'—C4"'—C5"' | 119.8 (2) |
N5'—C4'—C2"' | 120.39 (19) | C4"'—C5"'—C6"' | 117.6 (2) |
C3'—C4'—C2"' | 127.4 (2) | N1"'—C6"'—C5"' | 124.2 (2) |
N5—S1—N2—C3 | 0.78 (16) | C6"—N1"—C2"—C3" | −1.2 (3) |
S1—N2—C3—C4 | −0.7 (2) | C6"—N1"—C2"—C4 | 177.90 (19) |
S1—N2—C3—C3' | 178.60 (16) | N5—C4—C2"—N1" | 179.71 (18) |
N2—C3—C4—N5 | 0.3 (3) | C3—C4—C2"—N1" | −1.6 (3) |
C3'—C3—C4—N5 | −178.9 (2) | N5—C4—C2"—C3" | −1.2 (3) |
N2—C3—C4—C2" | −178.5 (2) | C3—C4—C2"—C3" | 177.5 (2) |
C3'—C3—C4—C2" | 2.3 (4) | N1"—C2"—C3"—C4" | 1.0 (3) |
C3—C4—N5—S1 | 0.3 (2) | C4—C2"—C3"—C4" | −178.1 (2) |
C2"—C4—N5—S1 | 179.16 (16) | C2"—C3"—C4"—C5" | −0.3 (3) |
N2—S1—N5—C4 | −0.62 (16) | C3"—C4"—C5"—C6" | 0.0 (3) |
N5'—S1'—N2'—C3' | 0.49 (15) | C2"—N1"—C6"—C5" | 0.8 (3) |
S1'—N2'—C3'—C4' | −0.3 (2) | C4"—C5"—C6"—N1" | −0.2 (4) |
S1'—N2'—C3'—C3 | −178.95 (14) | C6"'—N1"'—C2"'—C3"' | −0.7 (3) |
N2—C3—C3'—N2' | 83.5 (3) | C6"'—N1"'—C2"'—C4' | 177.12 (18) |
C4—C3—C3'—N2' | −97.3 (3) | N5'—C4'—C2"'—N1"' | −161.73 (18) |
N2—C3—C3'—C4' | −95.0 (3) | C3'—C4'—C2"'—N1"' | 18.6 (3) |
C4—C3—C3'—C4' | 84.2 (3) | N5'—C4'—C2"'—C3"' | 16.1 (3) |
N2'—C3'—C4'—N5' | −0.1 (2) | C3'—C4'—C2"'—C3"' | −163.48 (19) |
C3—C3'—C4'—N5' | 178.45 (18) | N1"'—C2"'—C3"'—C4"' | −0.4 (3) |
N2'—C3'—C4'—C2"' | 179.57 (19) | C4'—C2"'—C3"'—C4"' | −178.16 (19) |
C3—C3'—C4'—C2"' | −1.9 (3) | C2"'—C3"'—C4"'—C5"' | 1.3 (3) |
C3'—C4'—N5'—S1' | 0.4 (2) | C3"'—C4"'—C5"'—C6"' | −1.0 (3) |
C2"'—C4'—N5'—S1' | −179.26 (15) | C2"'—N1"'—C6"'—C5"' | 1.1 (3) |
N2'—S1'—N5'—C4' | −0.54 (15) | C4"'—C5"'—C6"'—N1"' | −0.2 (3) |
Experimental details
Crystal data | |
Chemical formula | C14H8N6S2 |
Mr | 324.38 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 163 |
a, b, c (Å) | 6.330 (5), 9.007 (7), 12.25 (1) |
α, β, γ (°) | 84.427 (9), 85.113 (9), 79.425 (9) |
V (Å3) | 681.6 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.40 |
Crystal size (mm) | 0.46 × 0.34 × 0.10 |
Data collection | |
Diffractometer | CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.827, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8929, 2772, 2016 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.627 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.099, 1.00 |
No. of reflections | 2772 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.28 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.
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We are currently studying the synthesis and metal complexes of new chelating and bridging heterocyclic ligands that incorporate less commonly encountered heterocyclic rings as donor subunits. For example, we have reported a number of chelating ligands which contain tetrazole (Downard et al., 1995), furoxan (Richardson & Steel, 2000a), benzisoxazole (Richardson & Steel, 2000b) and benzotriazole (Richardson & Steel, 2000c) rings. As part of this work, we have synthesized a number of ligands containing a 1,2,5-thiadiazole ring. Of the several synthetic methods for this ring system, the most general has been the reaction of disulfur dichloride with 1,2-diamines or dioximes (Weinstock et al., 1967). Recently, Rees and co-workers introduced a new efficient method for the synthesis of 1,2,5-thiadiazoles based on reactions of trithiazyl trichloride with alkenes and alkynes (Duan et al., 1996). They have further shown that this reaction is applicable to a range of substrates (Duan et al., 1997; Duan & Rees, 1997). We have utilized this method for the synthesis of the title compound, (I), which was prepared by reaction of S3N3Cl3 with 1,4-bis(2-pyridyl)buta-1,3-diyne. In view of our interest in the structures and conformations of biheterocycles (Steel, 1996a,b) and quaterheterocycles (Honey & Steel, 1991; Phillips & Steel, 1995), we have determined the X-ray crystal structure of (I) at 163 K. \sch
The ligand crystallizes in the triclinic space group P1, with one full molecule in the asymmetric unit (Fig. 1). Interestingly, the 1,2,5-thiadiazole rings are approximately orthogonal to each other [84.1 (1) °]. The two halves of the molecule differ in the conformations about the inter-ring bonds. Although both pyridine-thiadiazole bonds have s-trans conformations, in one half of the molecule the thiadiazole (S1—N5) and its attached pyridine ring (N1"-C6") are coplanar [2.9 (1) °], while for the other half there exists a slight twist of the pyridine away from the plane of the thiadiazole [17.7 (1) °]. Thus, there is conjugation of the π-systems within each pyridylthiadiazole subunit, but this does not extend over the whole molecule, due to the non-planarity of the central bithiadiazole subunit. The bonding geometry of each thiadiazole ring is similar to that found in 3,4-diphenyl-1,2,5-thiadiazole (Mellini & Merlino, 1976).
Inspection of the molecular packing reveals a number of relatively short intermolecular interactions. Firstly, the molecules associate into dimers through a pair of electrostatic interactions between electron deficient sulfur atoms (S1) and electron rich nitrogen atoms (N5) of two molecules related by a crystallographic centre of inversion [N—S 3.124 (2) Å]. These dimeric pairs further associate by S—N interactions of the same thiadiazole ring with the other thiadiazole ring of an adjacent molecule displaced one unit cell along the a axis [S1—N2' 3.302 (2) Å; N2—S1' 3.331 (2) Å]. These interactions (Fig. 2) are all less than the sum of the van der Waals radii of N and S (3.35 Å) and are similar in nature to those previously noted in structurally related molecules (Mellini & Merlino, 1976). In addition to these electrostatic interactions there are π-π stacking interactions (not shown in Fig. 2) between cofacial pyridine rings (N1"'-C6"') of molecules related by a centre of inversion and separated by 3.41 Å.
This represents the first stucture determination of a bi-1,2,5-thiadiazole (Steel, 1996a). Metal complexes of this new ligand will be reported elsewhere.