A new polymorph of 2,5 bis­­(4 pyrid­yl) 1,3,4 thia­diazole

organic papers

Acta Cryst.(2005). E61, o2547–o2548 doi:10.1107/S1600536805022142 Zhaoet al. _C

12H8N4S

o2547

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

A new polymorph of

2,5-bis(4-pyridyl)-1,3,4-thia-diazole

Xiao-Jun Zhao, Hua Cai and Miao Du*

College of Chemistry and Life Science, Tianjin Normal University, Tianjin 300074, People’s Republic of China

Correspondence e-mail: dumiao@public.tpt.tj.cn

Key indicators

Single-crystal X-ray study T= 293 K

Mean(C–C) = 0.003 A˚ Rfactor = 0.032 wRfactor = 0.101

Data-to-parameter ratio = 12.0

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

A new polymorph of 2,5-bis(4-pyridyl)-1,3,4-thiadiazole, C12H8N4S, obtained under hydrothermal conditions, is

described. In this structure, the two terminal pyridyl groups are inclined to the central thiadiazole ring with dihedral angles of 6.47 (2) and 29.95 (5)_{, and the dihedral angle between the}

pyridyl ring planes is 23.65 (6)_{. An intermolecular C—H N}

weak interaction is observed. The structural differences of two polymorphs of 2,5-bis(4-pyridyl)-1,3,4-thiadiazole are also discussed.

Comment

Recently, we have reported the crystal structure of 2,5-bis(4-pyridyl)-1,3,4-thiadiazole [form A, monoclinic, C2/c, with lattice parameters ofa= 26.179 (9) A˚ ,b= 5.8223 (17) A˚ ,c=

7.169 (3) A˚ and = 105.855 (9)_{], which is obtained by}

recrystallizing the commercial product from a hot CH3OH/

H2O solution (Duet al., 2004). During our efforts to

investi-gate the assembly of metal-organic coordination frameworks based on this bent dipyridyl linker, a new polymorph (formB), (I), was generated accidentally under hydrothermal condi-tions; the crystal structure of (I) is described in this paper.

The molecular structure of (I), shown in Fig. 1, contains no crystallographically imposed symmetry; however, a crystal-lographic twofold axis was detected in the structure of

poly-morph A. The two pyridyl rings make dihedral angles of

6.47 (2) and 29.95 (5)_{with the central thiadiazole system, and}

the dihedral angle between them is 23.65 (6)_{. The}

corre-sponding values in polymorph A are 21.8 (2), 21.8 (2) and

Received 23 June 2005 Accepted 11 July 2005 Online 16 July 2005

Figure 1

43.0 (2)_{, respectively. Selected bond lengths and angles are}

listed in Table 1. For the pyridyl rings, the C—N bond lengths (mean value 1.329 A˚ ), are within the range of values normally

considered standard for single C—N (1.47 A˚ ) and double

C N (1.28 A˚ ) bonds. The C—N bond lengths in the

thia-diazole ring are 1.302 (2) and 1.298 (2) A˚ . All these bond

geometries are comparable to those in polymorph A.

Addi-tionally, the angle between the center of the thiadiazole ring and the two pyridyl N-atom donors is 161_{, and the separation}

of these two N atoms is 10.785 (2) A˚ . The corresponding parameters in polymorphAare 156_{and 10.763 (4) A˚ .}

No significant interactions, such as hydrogen bonds or–

stacking, are observed in polymorph A. Notably, analysis of the crystal packing of this structure (polymorph B) suggests weak C2—H2 N4 intermolecular interactions, resulting in a one-dimensional chain along the [100] direction (Fig. 2). The relevant hydrogen-bonding parameters are listed in Table 2. Additionally, the interplanar distance between two layers of molecules is 3.5–3.8 A˚ , and the centroid-to-centroid distance is about 3.743 A˚ , indicating the existence of aromatic stacking

interactions. Examination of this structure with PLATON

(Spek, 2003) reveals no solvent-accessible voids in the unit cell.

Experimental

A mixture of Zn(OAc)24H2O (21.8 mg, 0.1 mmol), isophthalic acid

(16.8 mg, 0.10 mmol), and 2,5-bis(4-pyridyl)-1,3,4-thiadiazole (23.5 mg, 0.1 mmol) in water (10 ml) was heated at 433 K for 3 d in a sealed Teflon-lined stainless steel vessel (20 ml) under autogenous pressure. After the reaction mixture was slowly cooled to room temperature at a rate of 5 K h1_{, pale-yellow lamellar single crystals}

suitable for X-ray diffraction were produced.

Crystal data

C12H8N4S

Mr= 240.28

Monoclinic,P21=c

a= 13.395 (2) A˚

b= 7.1833 (11) A˚

c= 11.4151 (18) A˚

= 104.948 (2)

V= 1061.2 (3) A˚3

Z= 4

Dx= 1.504 Mg m3

MoKradiation Cell parameters from 1940

reflections

= 3.2–27.3

= 0.28 mm1

T= 293 (2) K Plate, pale yellow 0.300.240.08 mm

Data collection

Bruker APEX-II CCD area-detector diffractometer

’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.770,Tmax= 1.000 5414 measured reflections

1862 independent reflections 1515 reflections withI> 2(I)

Rint= 0.023

max= 25.0

h=15!15

k=8!4

l=13!13

Refinement

Refinement onF2

R[F2_{> 2(F}2_{)] = 0.032}

wR(F2_{) = 0.102}

S= 1.07 1862 reflections 155 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0679P)2 + 0.0172P]

whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.23 e A˚3 min=0.22 e A˚3

Extinction correction:SHELXL97

Table 1

Selected geometric parameters (A˚ ,_).

S1—C6 1.7141 (17)

S1—C7 1.7182 (18)

N1—C3 1.325 (2)

N1—C2 1.337 (2)

N2—C6 1.302 (2)

N2—N3 1.365 (2)

N3—C7 1.298 (2)

N4—C11 1.325 (3)

N4—C10 1.330 (3)

C6—S1—C7 86.79 (8)

C3—N1—C2 116.62 (16)

C6—N2—N3 112.18 (15)

C7—N3—N2 112.76 (15)

C11—N4—C10 116.29 (16)

C2—C1—C5 119.13 (16)

N1—C2—C1 123.72 (17)

N1—C3—C4 124.03 (17)

C3—C4—C5 118.91 (16)

C4—C5—C1 117.60 (16)

N2—C6—S1 114.29 (14)

N3—C7—S1 113.96 (13)

C9—C8—C12 117.51 (16)

C8—C9—C10 118.96 (18)

N4—C10—C9 124.13 (18)

N4—C11—C12 124.33 (17)

C11—C12—C8 118.76 (17)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

C2—H2 N4i

0.93 2.57 3.361 (3) 143

Symmetry code: (i)xþ1;y;z.

Although all H atoms were visible in difference Fourier maps, they were placed in geometrically calculated positions with C—H = 0.93 A˚ and included in the final refinement in the riding-model approxima-tion, with displacement parameters derived from their parent atoms [Uiso(H) = 1.2Ueq(C)].

Data collection:APEX-II(Bruker, 2003); cell refinement: APEX-II; data reduction:SAINT(Bruker, 2001); program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL (Bruker, 2001); software used to prepare material for publication:SHELXTL.

The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (grant No. 20401012), the Key Project of Tianjin Natural Science Foun-dation (grant No. 043804111) and Tianjin Normal University (to MD).

References

Bruker (2001). SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2003).APEX-II. Bruker AXS Inc., Madison, Wisconsin, USA. Du, M., Zhao, X.-J. & Li, C.-P. (2004).Acta Cryst.E60, o706–o707. Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Figure 2

supporting information

sup-1 Acta Cryst. (2005). E61, o2547–o2548

supporting information

Acta Cryst. (2005). E61, o2547–o2548 [https://doi.org/10.1107/S1600536805022142]

A new polymorph of 2,5-bis(4-pyridyl)-1,3,4-thiadiazole

Xiao-Jun Zhao, Hua Cai and Miao Du

2,5-bis(4-pyridyl)-1,3,4-thiadiazole

Crystal data

C12H8N4S Mr = 240.28 Monoclinic, P21/c Hall symbol: -P 2ybc a = 13.395 (2) Å b = 7.1833 (11) Å c = 11.4151 (18) Å β = 104.948 (2)° V = 1061.2 (3) Å3 Z = 4

F(000) = 496 Dx = 1.504 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1940 reflections θ = 3.2–27.3°

µ = 0.28 mm−1 T = 293 K

Lamellar, pale yellow 0.30 × 0.24 × 0.08 mm

Data collection

Bruker APEX-II CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.770, Tmax = 1.000

5414 measured reflections 1862 independent reflections 1515 reflections with I > 2σ(I) Rint = 0.023

θmax = 25.0°, θmin = 3.2° h = −15→15

k = −8→4 l = −13→13

Refinement

Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.032} wR(F2_{) = 0.102} S = 1.07 1862 reflections 155 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0679P)2 + 0.0172P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.23 e Å−3 Δρmin = −0.22 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 F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

S1 0.70555 (3) 0.13019 (6) 0.87463 (4) 0.0411 (2) N1 1.11893 (11) 0.1743 (2) 0.93303 (14) 0.0464 (4) N2 0.75023 (11) 0.1460 (2) 0.67143 (14) 0.0462 (4) N3 0.64493 (12) 0.1409 (2) 0.64481 (14) 0.0472 (4) N4 0.28675 (12) 0.1179 (2) 0.71677 (16) 0.0506 (4) C1 0.97174 (13) 0.0817 (2) 0.77593 (15) 0.0390 (4)

H1 0.9461 0.0253 0.7008 0.047*

C2 1.07654 (13) 0.0957 (3) 0.82551 (17) 0.0432 (5)

H2 1.1204 0.0477 0.7818 0.052*

C3 1.05425 (13) 0.2411 (2) 0.99306 (16) 0.0453 (5)

H3 1.0821 0.2961 1.0681 0.054*

C4 0.94792 (13) 0.2340 (2) 0.95096 (15) 0.0404 (4)

H4 0.9060 0.2830 0.9968 0.048*

C5 0.90482 (13) 0.1529 (2) 0.83938 (15) 0.0339 (4) C6 0.79231 (13) 0.1427 (2) 0.78771 (16) 0.0347 (4) C7 0.61030 (13) 0.1342 (2) 0.74097 (15) 0.0354 (4) C8 0.49930 (12) 0.1287 (2) 0.73569 (16) 0.0355 (4) C9 0.46184 (15) 0.1391 (2) 0.83724 (18) 0.0462 (5)

H9 0.5069 0.1503 0.9140 0.055*

C10 0.35611 (15) 0.1328 (3) 0.82321 (18) 0.0510 (5)

H10 0.3321 0.1394 0.8926 0.061*

C11 0.32375 (14) 0.1087 (3) 0.61987 (18) 0.0472 (5)

H11 0.2767 0.0991 0.5444 0.057*

C12 0.42750 (14) 0.1123 (2) 0.62359 (17) 0.0420 (4)

H12 0.4491 0.1040 0.5526 0.050*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-3 Acta Cryst. (2005). E61, o2547–o2548

C3 0.0401 (10) 0.0525 (11) 0.0399 (10) −0.0071 (8) 0.0041 (8) −0.0018 (8) C4 0.0382 (10) 0.0443 (10) 0.0403 (9) −0.0003 (7) 0.0131 (7) −0.0036 (7) C5 0.0293 (9) 0.0365 (9) 0.0367 (9) −0.0014 (6) 0.0096 (7) 0.0031 (7) C6 0.0304 (9) 0.0378 (9) 0.0370 (9) −0.0002 (7) 0.0107 (7) −0.0017 (7) C7 0.0303 (9) 0.0390 (9) 0.0375 (9) 0.0009 (7) 0.0097 (7) −0.0024 (7) C8 0.0293 (9) 0.0344 (9) 0.0433 (10) 0.0005 (7) 0.0100 (8) −0.0016 (7) C9 0.0374 (10) 0.0601 (12) 0.0419 (10) −0.0019 (8) 0.0112 (8) −0.0043 (8) C10 0.0427 (11) 0.0654 (13) 0.0513 (12) −0.0027 (9) 0.0239 (10) −0.0040 (9) C11 0.0327 (10) 0.0577 (12) 0.0489 (11) 0.0020 (8) 0.0062 (8) 0.0027 (9) C12 0.0342 (10) 0.0527 (11) 0.0397 (10) 0.0032 (7) 0.0106 (8) 0.0026 (8)

Geometric parameters (Å, º)

S1—C6 1.7141 (17) C3—H3 0.9300

S1—C7 1.7182 (18) C4—C5 1.384 (2)

N1—C3 1.325 (2) C4—H4 0.9300

N1—C2 1.337 (2) C5—C6 1.472 (2)

N2—C6 1.302 (2) C7—C8 1.473 (2)

N2—N3 1.365 (2) C8—C9 1.379 (3)

N3—C7 1.298 (2) C8—C12 1.393 (2)

N4—C11 1.325 (3) C9—C10 1.384 (3)

N4—C10 1.330 (3) C9—H9 0.9300

C1—C2 1.375 (2) C10—H10 0.9300

C1—C5 1.387 (2) C11—C12 1.379 (3)

C1—H1 0.9300 C11—H11 0.9300

C2—H2 0.9300 C12—H12 0.9300

C3—C4 1.382 (2)

C6—S1—C7 86.79 (8) N2—C6—S1 114.29 (14)

C3—N1—C2 116.62 (16) C5—C6—S1 123.21 (13)

C6—N2—N3 112.18 (15) N3—C7—C8 122.92 (16)

C7—N3—N2 112.76 (15) N3—C7—S1 113.96 (13)

C11—N4—C10 116.29 (16) C8—C7—S1 123.12 (13)

C2—C1—C5 119.13 (16) C9—C8—C12 117.51 (16)

C2—C1—H1 120.4 C9—C8—C7 123.13 (16)

C5—C1—H1 120.4 C12—C8—C7 119.36 (16)

N1—C2—C1 123.72 (17) C8—C9—C10 118.96 (18)

N1—C2—H2 118.1 C8—C9—H9 120.5

C1—C2—H2 118.1 C10—C9—H9 120.5

N1—C3—C4 124.03 (17) N4—C10—C9 124.13 (18)

N1—C3—H3 118.0 N4—C10—H10 117.9

C4—C3—H3 118.0 C9—C10—H10 117.9

C3—C4—C5 118.91 (16) N4—C11—C12 124.33 (17)

C3—C4—H4 120.5 N4—C11—H11 117.8

C5—C4—H4 120.5 C12—C11—H11 117.8

C4—C5—C1 117.60 (16) C11—C12—C8 118.76 (17)

C4—C5—C6 122.05 (15) C11—C12—H12 120.6

N2—C6—C5 122.49 (16)

C6—N2—N3—C7 0.1 (2) N2—N3—C7—C8 179.64 (14)

C3—N1—C2—C1 0.1 (3) N2—N3—C7—S1 −0.87 (19)

C5—C1—C2—N1 0.2 (3) C6—S1—C7—N3 1.04 (13)

C2—N1—C3—C4 −0.2 (3) C6—S1—C7—C8 −179.48 (13) N1—C3—C4—C5 0.0 (3) N3—C7—C8—C9 −173.72 (16)

C3—C4—C5—C1 0.3 (2) S1—C7—C8—C9 6.8 (2)

C3—C4—C5—C6 −179.06 (15) N3—C7—C8—C12 6.3 (2) C2—C1—C5—C4 −0.4 (2) S1—C7—C8—C12 −173.16 (13) C2—C1—C5—C6 179.00 (15) C12—C8—C9—C10 0.0 (2) N3—N2—C6—C5 −178.05 (14) C7—C8—C9—C10 −179.97 (15) N3—N2—C6—S1 0.71 (18) C11—N4—C10—C9 0.1 (3) C4—C5—C6—N2 149.13 (17) C8—C9—C10—N4 −0.3 (3) C1—C5—C6—N2 −30.2 (2) C10—N4—C11—C12 0.5 (3) C4—C5—C6—S1 −29.5 (2) N4—C11—C12—C8 −0.7 (3) C1—C5—C6—S1 151.11 (14) C9—C8—C12—C11 0.4 (2) C7—S1—C6—N2 −0.98 (13) C7—C8—C12—C11 −179.56 (15) C7—S1—C6—C5 177.77 (13)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C2—H2···N4i _{0.93 2.57 3.361 (3) 143}