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Acta Cryst. (2007). E63, m2381-m2382    [ doi:10.1107/S160053680704010X ]

(2,2'-Bipyridine-[kappa]2N,N')bis(5-thioxo-1,5-dihydro-1,3,4-thiadiazole-3-thiolato-[kappa]S)zinc(II)

X.-L. Zhang, Y.-E. Qiu, C.-L. Zhang and B.-W. Xin

Abstract top

In the crystal structure of the title compound, [Zn(C2HN2S3)2(C10H8N2)], a twofold rotation axis passes through the Zn atom and the midpoint of the C-C bond linking the two pyridine rings. The ZnII atom is located on a 21 axis and is coordinated by two thiolate S atoms of different 5-thioxo-1,5-dihydro-1,3,4-thiadiazole-3-thiolate ligands and two N atoms of a 2,2'-bipyridine ligand in a tetrahedral geometry, with a Zn-S distance of 2.3204 (8) Å and a Zn-N distance of 2.061 (2) Å. In addition, mononuclear molecules are linked together to form a one-dimensional chain by N-H...S hydrogen bonds.

Comment top

The structures of 2,5-dimercapto-1,3,4-thiodiazole (Bats, 1976) and some metal-complexes of it (Li et al., 2005; Mura et al., 1985; Ma et al., 2004a,b; Qiu et al., 2006; Tannai et al., 2003, 2005, 2006 and Tzeng et al., 2007) have been reported. In these complexes, different co-ligands were used and the 2,5-dimercapto-1,3,4-thiodiazole shows different coordination modes and valences. Herein, we report its neutral ZnII complex with 2,2'-bipyridine as a co-ligand, [Zn(C10H8N2)(C2HN2S3)2], (I).

As shown in Fig. 1, the title compound (I) has a mononuclear structure, in which the center Zn(II) atom lies on a 21 axis and is four-coordinated by two thiolato S donors of distinct 1,3,4-thiadiazole-3H-5-thione-2-thiolato ligands and two N atoms of one 2,2'-bipyridine. The related bond distances and angles are listed in Table 1. The 2,2'-bipyridine molecule is also of 21 axis symmetry and chelates to ZnII. Each 1,3,4-thiadiazole-3H-5-thione-2-thiolato ligand located on a general crystallographic position coordinates to one ZnII atom by one S atom. The dihedral angle between two 1,3,4-thiadiazole-3H-5-thione-2-thiolato ligands is 94.2 (2) °. In addition, in the crystal structure of (I) such mononuclear molecules were connected with each other to form a one-dimensional chain (Fig. 2) by N—H···S hydrogen bonds (Table 2).

Related literature top

For related crystal structures, see: Bats (1976); Li et al. (2005); Mura et al. (1985); Qiu et al. (2006); Tannai et al. (2003, 2005, 2006); Tzeng et al. (2007). For related literature, see: Ma et al. (2004a,b).

Experimental top

A mixture of ZnCl2 (27 mg, 0.2 mmol), 2,5-dimercapto-1,3,4-thiodiazole (60 mg, 0.4 mmol), 2,2'-bipyridine (31 mg, 0.2 mmol) and NaOH (16 mg, 0.4 mmol) in 10 ml of water was placed in a Teflon-lined stainless-steel Parr bomb that was heated at 423 K for 36 h. Yellowy crystals were collected after the bomb allowed to cool to room temperature during a period of 24 h. Yield, 35%. FT—IR (KBr pellets, cm−1): 3437 s, 2866 s, 1493 s, 1445m, 1272 s, 1123m, 1034 s, 764m, 709 s.

Refinement top

The C-bound H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2 Ueq(C). The N-bound H atom was located in Fourier difference maps and refined isotropically, with an N—H distance restraint of 0.90 (1) Å.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998) and SHELXTL (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 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The structure of (I). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (A) 1 − x, y, 3/2 + z]
[Figure 2] Fig. 2. A view of the title molecules linked together to form a one-dimensional chain by N—H···S hydrogen bonds.
(2,2'-Bipyridine-κ2N,N')bis(5-thioxo-1,5-dihydro-1,3,4- thiadiazole-3-thiolato-κS)zinc(II) top
Crystal data top
[Zn(C2HN2S3)2(C10H8N2)]F000 = 1048
Mr = 520.01Dx = 1.663 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2398 reflections
a = 16.265 (5) Åθ = 2.5–27.1º
b = 8.459 (3) ŵ = 1.80 mm−1
c = 15.140 (5) ÅT = 293 (2) K
β = 94.459 (5)ºBlock, yellow
V = 2076.8 (11) Å30.20 × 0.20 × 0.18 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1926 independent reflections
Radiation source: fine-focus sealed tube1519 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.025
T = 293(2) Kθmax = 25.5º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −18→19
Tmin = 0.898, Tmax = 1.000k = −10→8
5362 measured reflectionsl = −12→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.072  w = 1/[σ2(Fo2) + (0.0383P)2 + 0.8193P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
1926 reflectionsΔρmax = 0.23 e Å−3
127 parametersΔρmin = −0.32 e Å−3
1 restraintExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Zn(C2HN2S3)2(C10H8N2)]V = 2076.8 (11) Å3
Mr = 520.01Z = 4
Monoclinic, C2/cMo Kα
a = 16.265 (5) ŵ = 1.80 mm−1
b = 8.459 (3) ÅT = 293 (2) K
c = 15.140 (5) Å0.20 × 0.20 × 0.18 mm
β = 94.459 (5)º
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer		1926 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		1519 reflections with I > 2σ(I)
Tmin = 0.898, Tmax = 1.000Rint = 0.025
5362 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0281 restraint
wR(F2) = 0.072H atoms treated by a mixture of
independent and constrained refinement
S = 1.02Δρmax = 0.23 e Å−3
1926 reflectionsΔρmin = −0.32 e Å−3
127 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
Zn10.50000.57996 (4)0.75000.03989 (14)
S10.49436 (4)0.21183 (8)0.51132 (4)0.04524 (19)
S20.57283 (4)0.43839 (8)0.65050 (5)0.04630 (19)
S30.33274 (4)0.09665 (10)0.41761 (5)0.0593 (2)
N10.35803 (12)0.3258 (2)0.54091 (13)0.0417 (5)
N20.41163 (12)0.4103 (2)0.59810 (13)0.0418 (5)
N30.57461 (13)0.7660 (3)0.79288 (14)0.0479 (5)
C10.38719 (14)0.2145 (3)0.48950 (15)0.0409 (6)
C20.48732 (14)0.3636 (3)0.58965 (15)0.0372 (5)
C30.54328 (18)0.9097 (3)0.77031 (17)0.0541 (7)
C40.5915 (3)1.0451 (4)0.7835 (2)0.0848 (13)
H4A0.56961.14370.76790.102*
C50.6712 (3)1.0331 (6)0.8194 (3)0.1046 (17)
H5A0.70391.12280.82740.126*
C60.7020 (2)0.8877 (5)0.8433 (2)0.0919 (13)
H6A0.75560.87780.86870.110*
C70.65260 (18)0.7551 (4)0.8292 (2)0.0656 (8)
H7A0.67390.65630.84530.079*
H10.3047 (7)0.348 (3)0.5441 (16)0.046 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0350 (2)0.0344 (2)0.0502 (3)0.0000.00271 (18)0.000
S10.0391 (4)0.0501 (4)0.0471 (4)0.0024 (3)0.0076 (3)−0.0099 (3)
S20.0332 (3)0.0495 (4)0.0561 (4)−0.0012 (3)0.0031 (3)−0.0094 (3)
S30.0474 (4)0.0766 (5)0.0535 (4)−0.0024 (4)0.0024 (3)−0.0284 (4)
N10.0336 (11)0.0468 (12)0.0445 (12)0.0021 (10)0.0024 (9)−0.0077 (10)
N20.0384 (11)0.0428 (12)0.0439 (12)−0.0014 (9)0.0023 (9)−0.0082 (9)
N30.0484 (13)0.0469 (13)0.0497 (13)−0.0125 (10)0.0118 (10)−0.0061 (10)
C10.0392 (13)0.0466 (14)0.0375 (13)−0.0013 (11)0.0065 (10)−0.0026 (11)
C20.0378 (13)0.0364 (12)0.0377 (13)−0.0003 (11)0.0053 (10)0.0010 (11)
C30.0796 (19)0.0387 (14)0.0485 (16)−0.0105 (13)0.0337 (15)−0.0096 (12)
C40.143 (4)0.0446 (17)0.075 (2)−0.034 (2)0.062 (3)−0.0226 (16)
C50.131 (4)0.096 (3)0.095 (3)−0.075 (3)0.064 (3)−0.054 (3)
C60.072 (2)0.126 (3)0.081 (3)−0.058 (2)0.026 (2)−0.042 (2)
C70.0495 (17)0.078 (2)0.070 (2)−0.0203 (16)0.0100 (15)−0.0136 (17)
Geometric parameters (Å, °) top
Zn1—N32.061 (2)N3—C71.346 (3)
Zn1—N3i2.061 (2)N3—C31.351 (3)
Zn1—S22.3204 (8)C3—C41.394 (4)
Zn1—S2i2.3204 (8)C3—C3i1.492 (6)
S1—C11.749 (2)C4—C51.368 (6)
S1—C21.758 (2)C4—H4A0.9300
S2—C21.727 (2)C5—C61.366 (6)
S3—C11.677 (2)C5—H5A0.9300
N1—C11.332 (3)C6—C71.386 (4)
N1—N21.379 (3)C6—H6A0.9300
N1—H10.892 (10)C7—H7A0.9300
N2—C21.308 (3)
N3—Zn1—N3i80.43 (13)N2—C2—S2124.21 (18)
N3—Zn1—S2106.31 (6)N2—C2—S1113.41 (17)
N3i—Zn1—S2120.49 (6)S2—C2—S1122.36 (14)
N3—Zn1—S2i120.49 (6)N3—C3—C4120.4 (3)
N3i—Zn1—S2i106.31 (6)N3—C3—C3i115.44 (15)
S2—Zn1—S2i117.86 (4)C4—C3—C3i124.2 (2)
C1—S1—C290.09 (11)C5—C4—C3120.0 (4)
C2—S2—Zn196.01 (8)C5—C4—H4A120.0
C1—N1—N2119.8 (2)C3—C4—H4A120.0
C1—N1—H1125.1 (16)C6—C5—C4119.3 (3)
N2—N1—H1115.1 (16)C6—C5—H5A120.4
C2—N2—N1109.64 (19)C4—C5—H5A120.4
C7—N3—C3119.3 (2)C5—C6—C7119.4 (4)
C7—N3—Zn1126.1 (2)C5—C6—H6A120.3
C3—N3—Zn1113.94 (18)C7—C6—H6A120.3
N1—C1—S3127.25 (19)N3—C7—C6121.6 (3)
N1—C1—S1107.09 (17)N3—C7—H7A119.2
S3—C1—S1125.66 (15)C6—C7—H7A119.2
N3—Zn1—S2—C2−152.67 (11)Zn1—S2—C2—N210.1 (2)
N3i—Zn1—S2—C2−64.32 (11)Zn1—S2—C2—S1−168.23 (13)
S2i—Zn1—S2—C268.51 (8)C1—S1—C2—N20.18 (19)
C1—N1—N2—C21.1 (3)C1—S1—C2—S2178.71 (16)
N3i—Zn1—N3—C7−173.8 (3)C7—N3—C3—C40.8 (4)
S2—Zn1—N3—C7−54.7 (2)Zn1—N3—C3—C4−170.8 (2)
S2i—Zn1—N3—C782.8 (2)C7—N3—C3—C3i179.4 (3)
N3i—Zn1—N3—C3−2.92 (13)Zn1—N3—C3—C3i7.8 (3)
S2—Zn1—N3—C3116.21 (17)N3—C3—C4—C50.1 (4)
S2i—Zn1—N3—C3−106.29 (17)C3i—C3—C4—C5−178.4 (3)
N2—N1—C1—S3178.57 (18)C3—C4—C5—C6−1.1 (5)
N2—N1—C1—S1−0.9 (3)C4—C5—C6—C71.2 (5)
C2—S1—C1—N10.40 (18)C3—N3—C7—C6−0.7 (4)
C2—S1—C1—S3−179.12 (18)Zn1—N3—C7—C6169.8 (2)
N1—N2—C2—S2−179.18 (17)C5—C6—C7—N3−0.3 (5)
N1—N2—C2—S1−0.7 (2)
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S3ii0.892 (10)2.399 (11)3.280 (2)169 (2)
Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Zn1—N32.061 (2)S3—C11.677 (2)
Zn1—S22.3204 (8)N1—C11.332 (3)
S1—C11.749 (2)N1—N21.379 (3)
S1—C21.758 (2)N1—H10.892 (10)
S2—C21.727 (2)N2—C21.308 (3)
N3—Zn1—N3i80.43 (13)S2—Zn1—S2i117.86 (4)
N3—Zn1—S2106.31 (6)C2—S2—Zn196.01 (8)
N3i—Zn1—S2120.49 (6)
Symmetry codes: (i) −x+1, y, −z+3/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···S3ii0.892 (10)2.399 (11)3.280 (2)169 (2)
Symmetry codes: (ii) −x+1/2, −y+1/2, −z+1.
Acknowledgements top

The authors thank Dr Jianrong Li of Nankai University for discussion and Dezhou University for supporting this work.

references
References top

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