(2,2′-Bipyridine-κ²N,N′)bis­(5-thioxo-1,5-dihydro-1,3,4-thia­diazole-3-thiol­ato-κS)­zinc(II)

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 Zn^II 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.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.027
• wR factor = 0.072
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.72
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.81 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C5
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.03

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.724
            Tmax scaled      0.724 Tmin scaled      0.650
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.87
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   5 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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 Zn^II 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 Zn^II. Each 1,3,4-thiadiazole-3H-5-thione-2-thiolato ligand located on a general crystallographic position coordinates to one Zn^II 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

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).

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.2 U_eq(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

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

	Fig. 1. The structure of (I). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (A) 1 - x, y, 3/2 + z]
	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)

Crystal data

[Zn(C2HN2S3)2(C10H8N2)]	F(000) = 1048
Mr = 520.01	Dx = 1.663 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2398 reflections
a = 16.265 (5) Å	θ = 2.5–27.1°
b = 8.459 (3) Å	µ = 1.80 mm^−1
c = 15.140 (5) Å	T = 293 K
β = 94.459 (5)°	Block, yellow
V = 2076.8 (11) Å^3	0.20 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART 1000 CCD area-detector diffractometer	1926 independent reflections
Radiation source: fine-focus sealed tube	1519 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −18→19
Tmin = 0.898, Tmax = 1.000	k = −10→8
5362 measured reflections	l = −12→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0383P)^2 + 0.8193P] where P = (Fo^2 + 2Fc^2)/3
1926 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.23 e Å^−3
1 restraint	Δρmin = −0.32 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 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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.5000	0.57996 (4)	0.7500	0.03989 (14)
S1	0.49436 (4)	0.21183 (8)	0.51132 (4)	0.04524 (19)
S2	0.57283 (4)	0.43839 (8)	0.65050 (5)	0.04630 (19)
S3	0.33274 (4)	0.09665 (10)	0.41761 (5)	0.0593 (2)
N1	0.35803 (12)	0.3258 (2)	0.54091 (13)	0.0417 (5)
N2	0.41163 (12)	0.4103 (2)	0.59810 (13)	0.0418 (5)
N3	0.57461 (13)	0.7660 (3)	0.79288 (14)	0.0479 (5)
C1	0.38719 (14)	0.2145 (3)	0.48950 (15)	0.0409 (6)
C2	0.48732 (14)	0.3636 (3)	0.58965 (15)	0.0372 (5)
C3	0.54328 (18)	0.9097 (3)	0.77031 (17)	0.0541 (7)
C4	0.5915 (3)	1.0451 (4)	0.7835 (2)	0.0848 (13)
H4A	0.5696	1.1437	0.7679	0.102*
C5	0.6712 (3)	1.0331 (6)	0.8194 (3)	0.1046 (17)
H5A	0.7039	1.1228	0.8274	0.126*
C6	0.7020 (2)	0.8877 (5)	0.8433 (2)	0.0919 (13)
H6A	0.7556	0.8778	0.8687	0.110*
C7	0.65260 (18)	0.7551 (4)	0.8292 (2)	0.0656 (8)
H7A	0.6739	0.6563	0.8453	0.079*
H1	0.3047 (7)	0.348 (3)	0.5441 (16)	0.046 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0350 (2)	0.0344 (2)	0.0502 (3)	0.000	0.00271 (18)	0.000
S1	0.0391 (4)	0.0501 (4)	0.0471 (4)	0.0024 (3)	0.0076 (3)	−0.0099 (3)
S2	0.0332 (3)	0.0495 (4)	0.0561 (4)	−0.0012 (3)	0.0031 (3)	−0.0094 (3)
S3	0.0474 (4)	0.0766 (5)	0.0535 (4)	−0.0024 (4)	0.0024 (3)	−0.0284 (4)
N1	0.0336 (11)	0.0468 (12)	0.0445 (12)	0.0021 (10)	0.0024 (9)	−0.0077 (10)
N2	0.0384 (11)	0.0428 (12)	0.0439 (12)	−0.0014 (9)	0.0023 (9)	−0.0082 (9)
N3	0.0484 (13)	0.0469 (13)	0.0497 (13)	−0.0125 (10)	0.0118 (10)	−0.0061 (10)
C1	0.0392 (13)	0.0466 (14)	0.0375 (13)	−0.0013 (11)	0.0065 (10)	−0.0026 (11)
C2	0.0378 (13)	0.0364 (12)	0.0377 (13)	−0.0003 (11)	0.0053 (10)	0.0010 (11)
C3	0.0796 (19)	0.0387 (14)	0.0485 (16)	−0.0105 (13)	0.0337 (15)	−0.0096 (12)
C4	0.143 (4)	0.0446 (17)	0.075 (2)	−0.034 (2)	0.062 (3)	−0.0226 (16)
C5	0.131 (4)	0.096 (3)	0.095 (3)	−0.075 (3)	0.064 (3)	−0.054 (3)
C6	0.072 (2)	0.126 (3)	0.081 (3)	−0.058 (2)	0.026 (2)	−0.042 (2)
C7	0.0495 (17)	0.078 (2)	0.070 (2)	−0.0203 (16)	0.0100 (15)	−0.0136 (17)

Geometric parameters (Å, º)

Zn1—N3	2.061 (2)	N3—C7	1.346 (3)
Zn1—N3^i	2.061 (2)	N3—C3	1.351 (3)
Zn1—S2	2.3204 (8)	C3—C4	1.394 (4)
Zn1—S2^i	2.3204 (8)	C3—C3^i	1.492 (6)
S1—C1	1.749 (2)	C4—C5	1.368 (6)
S1—C2	1.758 (2)	C4—H4A	0.9300
S2—C2	1.727 (2)	C5—C6	1.366 (6)
S3—C1	1.677 (2)	C5—H5A	0.9300
N1—C1	1.332 (3)	C6—C7	1.386 (4)
N1—N2	1.379 (3)	C6—H6A	0.9300
N1—H1	0.892 (10)	C7—H7A	0.9300
N2—C2	1.308 (3)
N3—Zn1—N3^i	80.43 (13)	N2—C2—S2	124.21 (18)
N3—Zn1—S2	106.31 (6)	N2—C2—S1	113.41 (17)
N3^i—Zn1—S2	120.49 (6)	S2—C2—S1	122.36 (14)
N3—Zn1—S2^i	120.49 (6)	N3—C3—C4	120.4 (3)
N3^i—Zn1—S2^i	106.31 (6)	N3—C3—C3^i	115.44 (15)
S2—Zn1—S2^i	117.86 (4)	C4—C3—C3^i	124.2 (2)
C1—S1—C2	90.09 (11)	C5—C4—C3	120.0 (4)
C2—S2—Zn1	96.01 (8)	C5—C4—H4A	120.0
C1—N1—N2	119.8 (2)	C3—C4—H4A	120.0
C1—N1—H1	125.1 (16)	C6—C5—C4	119.3 (3)
N2—N1—H1	115.1 (16)	C6—C5—H5A	120.4
C2—N2—N1	109.64 (19)	C4—C5—H5A	120.4
C7—N3—C3	119.3 (2)	C5—C6—C7	119.4 (4)
C7—N3—Zn1	126.1 (2)	C5—C6—H6A	120.3
C3—N3—Zn1	113.94 (18)	C7—C6—H6A	120.3
N1—C1—S3	127.25 (19)	N3—C7—C6	121.6 (3)
N1—C1—S1	107.09 (17)	N3—C7—H7A	119.2
S3—C1—S1	125.66 (15)	C6—C7—H7A	119.2
N3—Zn1—S2—C2	−152.67 (11)	Zn1—S2—C2—N2	10.1 (2)
N3^i—Zn1—S2—C2	−64.32 (11)	Zn1—S2—C2—S1	−168.23 (13)
S2^i—Zn1—S2—C2	68.51 (8)	C1—S1—C2—N2	0.18 (19)
C1—N1—N2—C2	1.1 (3)	C1—S1—C2—S2	178.71 (16)
N3^i—Zn1—N3—C7	−173.8 (3)	C7—N3—C3—C4	0.8 (4)
S2—Zn1—N3—C7	−54.7 (2)	Zn1—N3—C3—C4	−170.8 (2)
S2^i—Zn1—N3—C7	82.8 (2)	C7—N3—C3—C3^i	179.4 (3)
N3^i—Zn1—N3—C3	−2.92 (13)	Zn1—N3—C3—C3^i	7.8 (3)
S2—Zn1—N3—C3	116.21 (17)	N3—C3—C4—C5	0.1 (4)
S2^i—Zn1—N3—C3	−106.29 (17)	C3^i—C3—C4—C5	−178.4 (3)
N2—N1—C1—S3	178.57 (18)	C3—C4—C5—C6	−1.1 (5)
N2—N1—C1—S1	−0.9 (3)	C4—C5—C6—C7	1.2 (5)
C2—S1—C1—N1	0.40 (18)	C3—N3—C7—C6	−0.7 (4)
C2—S1—C1—S3	−179.12 (18)	Zn1—N3—C7—C6	169.8 (2)
N1—N2—C2—S2	−179.18 (17)	C5—C6—C7—N3	−0.3 (5)
N1—N2—C2—S1	−0.7 (2)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S3^ii	0.89 (1)	2.40 (1)	3.280 (2)	169 (2)

Symmetry code: (ii) −x+1/2, −y+1/2, −z+1.