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The title compound, C14H8N6S2, crystallizes with the planes of the two central 1,2,5-thia­diazo­le rings orthogonal and with the pyridine rings approximately coplanar with their attached 1,2,5-thia­diazo­le rings.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100017431/de1157sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100017431/de1157Isup2.hkl
Contains datablock I

CCDC reference: 160003

Comment top

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.

Related literature top

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).

Experimental top

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.

Refinement top

Crystal decay was monitored by the measurement of duplicate reflections.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Perspective view and atom labelling of the structure of (I). Displacement ellipsoids are drawn at the 50% probability level and hydrogen atoms as circles of arbitrary radius.
[Figure 2] Fig. 2. Crystal packing showing intermolecular S—N interactions. Hydrogen atoms are not shown.
4,4'-Di(2-pyridyl)-3,3'-bi-1,2,5-thiadiazole top
Crystal data top
C14H8N6S2Z = 2
Mr = 324.38F(000) = 332
Triclinic, P1Dx = 1.580 Mg m3
a = 6.330 (5) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.007 (7) ÅCell parameters from 2500 reflections
c = 12.25 (1) Åθ = 2.8–26.3°
α = 84.427 (9)°µ = 0.40 mm1
β = 85.113 (9)°T = 163 K
γ = 79.425 (9)°Fragment, colourless
V = 681.6 (9) Å30.46 × 0.34 × 0.10 mm
Data collection top
CCD area detector
diffractometer
2772 independent reflections
Radiation source: fine-focus sealed tube2016 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 8.192 pixels mm-1θmax = 26.5°, θmin = 2.3°
ϕ and ω scansh = 77
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
k = 1111
Tmin = 0.827, Tmax = 1.000l = 1515
8929 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-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 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C14H8N6S2γ = 79.425 (9)°
Mr = 324.38V = 681.6 (9) Å3
Triclinic, P1Z = 2
a = 6.330 (5) ÅMo Kα radiation
b = 9.007 (7) ŵ = 0.40 mm1
c = 12.25 (1) ÅT = 163 K
α = 84.427 (9)°0.46 × 0.34 × 0.10 mm
β = 85.113 (9)°
Data collection top
CCD area detector
diffractometer
2772 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
2016 reflections with I > 2σ(I)
Tmin = 0.827, Tmax = 1.000Rint = 0.039
8929 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.00Δρmax = 0.31 e Å3
2772 reflectionsΔρmin = 0.28 e Å3
199 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
xyzUiso*/Ueq
S11.02092 (10)1.47534 (6)0.65833 (4)0.02750 (17)
N21.1480 (3)1.4958 (2)0.76517 (14)0.0262 (4)
C31.2951 (4)1.5803 (2)0.73078 (16)0.0221 (5)
C41.2979 (3)1.6236 (2)0.61533 (16)0.0215 (5)
N51.1510 (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"1.32321.70440.40060.035*
C4"1.5715 (4)1.8219 (3)0.37657 (19)0.0350 (6)
H4"1.56651.84180.29920.042*
C5"1.7224 (4)1.8737 (3)0.43202 (19)0.0328 (6)
H5"1.82261.92970.39320.039*
C6"1.7244 (4)1.8425 (2)0.54456 (19)0.0313 (6)
H6"1.82881.87820.58160.038*
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"'1.35222.04130.92790.034*
C4"'1.0552 (4)2.1448 (3)0.88290 (17)0.0317 (6)
H4"'1.06102.24110.90690.038*
C5"'0.8734 (4)2.1217 (3)0.83603 (18)0.0318 (6)
H5"'0.75182.20030.82820.038*
C6"'0.8753 (4)1.9786 (3)0.80072 (17)0.0311 (6)
H6"'0.75091.96210.76880.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0316 (4)0.0315 (3)0.0229 (3)0.0141 (3)0.0007 (2)0.0040 (2)
N20.0324 (12)0.0269 (10)0.0217 (10)0.0116 (9)0.0006 (8)0.0045 (8)
C30.0258 (13)0.0195 (11)0.0214 (11)0.0053 (9)0.0020 (9)0.0044 (8)
C40.0226 (12)0.0206 (11)0.0216 (11)0.0035 (9)0.0008 (9)0.0039 (8)
N50.0277 (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)
Geometric parameters (Å, º) top
S1—N51.6202 (19)N1"—C6"1.343 (3)
S1—N21.635 (2)N1"—C2"1.346 (3)
N2—C31.325 (3)C2"—C3"1.393 (3)
C3—C41.430 (3)C3"—C4"1.380 (3)
C3—C3'1.488 (3)C4"—C5"1.388 (3)
C4—N51.334 (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—N298.96 (11)C4'—N5'—S1'108.04 (15)
C3—N2—S1107.35 (15)C6"—N1"—C2"116.51 (19)
N2—C3—C4113.15 (19)N1"—C2"—C3"123.70 (19)
N2—C3—C3'118.53 (18)N1"—C2"—C4116.31 (19)
C4—C3—C3'128.32 (18)C3"—C2"—C4120.0 (2)
N5—C4—C3113.15 (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—S1107.39 (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'—C3119.54 (19)C3"'—C2"'—C4'121.4 (2)
C4'—C3'—C3126.8 (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—C30.78 (16)C6"—N1"—C2"—C3"1.2 (3)
S1—N2—C3—C40.7 (2)C6"—N1"—C2"—C4177.90 (19)
S1—N2—C3—C3'178.60 (16)N5—C4—C2"—N1"179.71 (18)
N2—C3—C4—N50.3 (3)C3—C4—C2"—N1"1.6 (3)
C3'—C3—C4—N5178.9 (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—S10.3 (2)C4—C2"—C3"—C4"178.1 (2)
C2"—C4—N5—S1179.16 (16)C2"—C3"—C4"—C5"0.3 (3)
N2—S1—N5—C40.62 (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'—C3178.95 (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 formulaC14H8N6S2
Mr324.38
Crystal system, space groupTriclinic, 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)
V3)681.6 (9)
Z2
Radiation typeMo Kα
µ (mm1)0.40
Crystal size (mm)0.46 × 0.34 × 0.10
Data collection
DiffractometerCCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.827, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8929, 2772, 2016
Rint0.039
(sin θ/λ)max1)0.627
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.099, 1.00
No. of reflections2772
No. of parameters199
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.28

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.

 

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