4,4′ Bi­pyridine–5 amino 1,3,4 thia­diazole 2(3H) thione (1/2)

organic papers

Acta Cryst.(2005). E61, o2239–o2240 doi:10.1107/S1600536805019136 Denget al. _C

10H8N22C2H3N3S2

o2239

Structure Reports Online

ISSN 1600-5368

4,4

_{-Bipyridine–5-amino-1,3,4-thiadiazole-2(3}

_H

)-thione (1/2)

Qian-Jun Deng,a,bMin-Xia Yaoa and Ming-Hua Zenga*

a

Department of Chemistry, Guangxi Normal University, Guilin 541000, Guangxi, People’s Republic of China, andb_{Science School, Foshan}

University, Foshan 528000, Guangdong, People’s Republic of China

Correspondence e-mail: zmhzsu@163.com

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C–C) = 0.004 A˚

Rfactor = 0.044

wRfactor = 0.109

Data-to-parameter ratio = 15.7

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

In the title complex, C10H8N22C2H3N3S2, the 4,40-bipyridine

(bpy) molecule, lying on an inversion centre, is connected to two 5-amino-1,3,4-thiadiazole-2(3H)-thione (tdz) molecules

through N—H N hydrogen bonds. The tdz planes are

slightly twisted with respect to the bpy plane, with a dihedral angle of 2.1 (2)_{. Further intermolecular N—H N and N—}

H S hydrogen bonds result in a three-dimensional network structure.

Comment

The title compound, (I), was prepared as part of our ongoing studies of hydrogen-bonding interactions in crystal structures (Sunet al., 2004). We report here the structure of 4,40

-bipyri-dine–5-amino-1,3,4-thiadiazole-2(3H)-thione (1/2), (I).

In (I), the 4,40_{-bipyridine (bpy) molecules, lying on an}

inversion centre, is connected to two

5-amino-1,3,4-thia-diazole-2(3H)-thione (tdz) molecules through N—H N

hydrogen bonds (Fig. 1 and Table 1). The tdz planes are slightly twisted with respect to the bpy plane, with a dihedral angle of only 2.1 (2)_{. The bpy–tdz (1/2) units are linked by}

N—H N hydrogen bonds to form a one-dimensional stair-like chain (Fig. 2). These chains are further interconnected by N—H S hydrogen bonds, leading to a three-dimensional network (Fig. 3).

Experimental

4,40_{-Bipyridine (0.1 mmol) and 5-amino-1,3,4-thiadiazole-2(3H} )-thione (0.2 mmol) were dissolved in a water–ethanol (4:1v/v, 10 ml) mixture. The solution was stirred for 1 h at 313 K and then filtered.

Received 6 June 2005 Accepted 15 June 2005 Online 24 June 2005

Figure 1

The resulting solution was allowed to stand in air at room tempera-ture for two days and yielded pale-yellow crystals.

Crystal data

C10H8N22C2H3N3S2

Mr= 422.57

Monoclinic,P2₁=n a= 7.020 (3) A˚ b= 8.121 (4) A˚ c= 16.888 (7) A˚

= 100.74 (4) V= 945.9 (7) A˚3 Z= 2

Dx= 1.484 Mg m

3 MoKradiation Cell parameters from 25

reflections

= 2–7

= 0.52 mm1 T= 293 (2) K Block, pale yellow 0.460.380.32 mm

Data collection

SiemensR3mdiffractometer

!scans

Absorption correction: scan (Northet al., 1968) Tmin= 0.796,Tmax= 0.852 2007 measured reflections 1852 independent reflections 1330 reflections withI> 2(I)

Rint= 0.046

max= 26.0

h= 0!8 k= 0!10 l=20!20 2 standard reflections

every 200 reflections intensity decay: none

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.044}

wR(F2_{) = 0.109}

S= 1.01 1852 reflections 118 parameters

H-atom parameters constrained

w= 1/[2

(Fo2) + (0.0451P)2 + 0.5922P]

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

max= 0.19 e A˚

3

min=0.23 e A˚

3

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N1—H1A N4 0.86 1.94 2.792 (3) 172 N3—H3A N2i

0.86 2.28 3.079 (4) 155 N3—H3B S2ii 0.86 2.57 3.412 (3) 165

Symmetry codes: (i)x;yþ2;z; (ii)xþ1

2;yþ12;zþ12.

H atoms were positioned geometrically (C—H = 0.93 A˚ and N— H = 0.86 A˚ ) and refined as riding on their parent atoms, withUiso(H) = 1.2Ueq(C, N).

Data collection:R3m Software (Siemens, 1990); cell refinement:

R3m Software; data reduction: R3m Software; program(s) used to solve structure:SHELXTL(Bruker, 1999); program(s) used to refine structure:SHELXTL; molecular graphics:SHELXTL; software used to prepare material for publication:SHELXTL.

We thank the Guangxi Normal University for supporting this study.

References

Bruker (1999). SHELXTL. Version 6.14. Bruker AXS Inc., Madison, Wisconsin, USA.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351– 359.

Siemens (1990). R3m Software. Version 4.0. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sun, X.-Z., Zeng, M.-H. & Ye, B.-H. (2004).Acta Cryst.E60, o2103–o2104. Figure 2

Perspective view, along thecaxis, of the chains. Hydrogen bonds shown as dashed lines.

Figure 3

supporting information

sup-1 Acta Cryst. (2005). E61, o2239–o2240

supporting information

Acta Cryst. (2005). E61, o2239–o2240 [https://doi.org/10.1107/S1600536805019136]

4,4

′

-Bipyridine

–

5-amino-1,3,4-thiadiazole-2(3

H

)-thione (1/2)

Qian-Jun Deng, Min-Xia Yao and Ming-Hua Zeng

Bipyridine bis[5-amino-1,3,4-thiadiazole-2(3H)-thione]

Crystal data

C10H8N2·2C2H3N3S2 Mr = 422.57

Monoclinic, P21/n

Hall symbol: -P 2yn

a = 7.020 (3) Å

b = 8.121 (4) Å

c = 16.888 (7) Å

β = 100.74 (4)°

V = 945.9 (7) Å3 Z = 2

F(000) = 436

Dx = 1.484 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections

θ = 2–7°

µ = 0.52 mm−1 T = 293 K

Block, pale yellow 0.46 × 0.38 × 0.32 mm

Data collection

Siemens R3m diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: ψ scan (North et al., 1968)

Tmin = 0.796, Tmax = 0.852

2007 measured reflections

1852 independent reflections 1330 reflections with I > 2σ(I)

Rint = 0.046

θmax = 26.0°, θmin = 2.5° h = 0→8

k = 0→10

l = −20→20

2 standard reflections every 200 reflections intensity decay: none

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.044} wR(F2_{) = 0.109} S = 1.01 1852 reflections 118 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) + (0.0451P)2 + 0.5922P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.19 e Å−3

Δρmin = −0.23 e Å−3

Special details

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 0.16290 (10) 0.83746 (11) 0.21733 (4) 0.0471 (2) S2 −0.12679 (12) 0.59067 (14) 0.26239 (5) 0.0664 (3) N1 −0.1564 (3) 0.7800 (3) 0.12878 (13) 0.0424 (6)

H1A −0.2694 0.7401 0.1103 0.051*

N2 −0.0759 (3) 0.8964 (3) 0.08449 (14) 0.0440 (6)

N3 0.2110 (4) 1.0489 (3) 0.09777 (15) 0.0560 (7)

H3A 0.1739 1.0962 0.0519 0.067*

H3B 0.3222 1.0723 0.1265 0.067*

N4 −0.5277 (3) 0.6752 (3) 0.05771 (15) 0.0474 (6) C1 −0.0582 (4) 0.7305 (4) 0.19978 (17) 0.0437 (7)

C2 0.0948 (4) 0.9382 (4) 0.12462 (16) 0.0407 (7)

C3 −0.6451 (4) 0.7150 (4) −0.0113 (2) 0.0558 (9)

H3C −0.6007 0.7915 −0.0447 0.067*

C4 −0.8275 (4) 0.6498 (4) −0.03628 (19) 0.0512 (8)

H4B −0.9017 0.6822 −0.0853 0.061*

C5 −0.9012 (4) 0.5361 (4) 0.01141 (16) 0.0368 (6) C6 −0.7789 (4) 0.4926 (4) 0.08262 (18) 0.0504 (8)

H6A −0.8194 0.4159 0.1168 0.060*

C7 −0.5972 (4) 0.5630 (5) 0.10289 (19) 0.0564 (9)

H7A −0.5184 0.5303 0.1508 0.068*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-3 Acta Cryst. (2005). E61, o2239–o2240

Geometric parameters (Å, º)

S1—C2 1.752 (3) N4—C7 1.337 (4)

S1—C1 1.755 (3) C3—C4 1.377 (4)

S2—C1 1.682 (3) C3—H3C 0.9300

N1—C1 1.329 (4) C4—C5 1.387 (4)

N1—N2 1.389 (3) C4—H4B 0.9300

N1—H1A 0.8600 C5—C6 1.387 (4)

N2—C2 1.307 (3) C5—C5i _{1.489 (5)}

N3—C2 1.348 (4) C6—C7 1.381 (4)

N3—H3A 0.8600 C6—H6A 0.9300

N3—H3B 0.8600 C7—H7A 0.9300

N4—C3 1.336 (4)

C2—S1—C1 89.69 (14) N4—C3—C4 124.1 (3)

C1—N1—N2 119.8 (2) N4—C3—H3C 117.9

C1—N1—H1A 120.1 C4—C3—H3C 117.9

N2—N1—H1A 120.1 C3—C4—C5 120.3 (3)

C2—N2—N1 108.9 (2) C3—C4—H4B 119.9

C2—N3—H3A 120.0 C5—C4—H4B 119.9

C2—N3—H3B 120.0 C6—C5—C4 115.8 (2)

H3A—N3—H3B 120.0 C6—C5—C5i _{121.4 (3)}

C3—N4—C7 115.6 (3) C4—C5—C5i _{122.8 (3)}

N1—C1—S2 127.6 (2) C7—C6—C5 120.2 (3)

N1—C1—S1 107.2 (2) C7—C6—H6A 119.9

S2—C1—S1 125.15 (17) C5—C6—H6A 119.9

N2—C2—N3 123.6 (3) N4—C7—C6 123.9 (3)

N2—C2—S1 114.4 (2) N4—C7—H7A 118.0

N3—C2—S1 122.0 (2) C6—C7—H7A 118.0

C1—N1—N2—C2 −0.1 (4) C7—N4—C3—C4 0.9 (5)

N2—N1—C1—S2 −179.3 (2) N4—C3—C4—C5 0.5 (5)

N2—N1—C1—S1 0.1 (3) C3—C4—C5—C6 −1.3 (5)

C2—S1—C1—N1 −0.1 (2) C3—C4—C5—C5i _{178.7 (3)}

C2—S1—C1—S2 179.4 (2) C4—C5—C6—C7 0.8 (5)

N1—N2—C2—N3 179.8 (3) C5i_{—C5—C6—C7 −179.2 (3)}

N1—N2—C2—S1 0.0 (3) C3—N4—C7—C6 −1.4 (5)

C1—S1—C2—N2 0.0 (2) C5—C6—C7—N4 0.6 (5)

C1—S1—C2—N3 −179.8 (3)

Symmetry code: (i) −x−2, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N3—H3A···N2ii _{0.86 2.28 3.079 (4) 155}

N3—H3B···S2iii _{0.86 2.57 3.412 (3) 165}