Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704010X/at2375sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704010X/at2375Isup2.hkl |
CCDC reference: 660138
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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).
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.
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.
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).
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).
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).
[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) Å3 | 0.20 × 0.20 × 0.18 mm |
Z = 4 |
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 on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0383P)2 + 0.8193P] where P = (Fo2 + 2Fc2)/3 |
1926 reflections | (Δ/σ)max < 0.001 |
127 parameters | Δρmax = 0.23 e Å−3 |
1 restraint | Δρmin = −0.32 e Å−3 |
[Zn(C2HN2S3)2(C10H8N2)] | V = 2076.8 (11) Å3 |
Mr = 520.01 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.265 (5) Å | µ = 1.80 mm−1 |
b = 8.459 (3) Å | T = 293 K |
c = 15.140 (5) Å | 0.20 × 0.20 × 0.18 mm |
β = 94.459 (5)° |
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 = 1.000 | Rint = 0.025 |
5362 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 1 restraint |
wR(F2) = 0.072 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.23 e Å−3 |
1926 reflections | Δρmin = −0.32 e Å−3 |
127 parameters |
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. |
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)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
Zn1—N3 | 2.061 (2) | N3—C7 | 1.346 (3) |
Zn1—N3i | 2.061 (2) | N3—C3 | 1.351 (3) |
Zn1—S2 | 2.3204 (8) | C3—C4 | 1.394 (4) |
Zn1—S2i | 2.3204 (8) | C3—C3i | 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—N3i | 80.43 (13) | N2—C2—S2 | 124.21 (18) |
N3—Zn1—S2 | 106.31 (6) | N2—C2—S1 | 113.41 (17) |
N3i—Zn1—S2 | 120.49 (6) | S2—C2—S1 | 122.36 (14) |
N3—Zn1—S2i | 120.49 (6) | N3—C3—C4 | 120.4 (3) |
N3i—Zn1—S2i | 106.31 (6) | N3—C3—C3i | 115.44 (15) |
S2—Zn1—S2i | 117.86 (4) | C4—C3—C3i | 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) |
N3i—Zn1—S2—C2 | −64.32 (11) | Zn1—S2—C2—S1 | −168.23 (13) |
S2i—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) |
N3i—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) |
S2i—Zn1—N3—C7 | 82.8 (2) | C7—N3—C3—C3i | 179.4 (3) |
N3i—Zn1—N3—C3 | −2.92 (13) | Zn1—N3—C3—C3i | 7.8 (3) |
S2—Zn1—N3—C3 | 116.21 (17) | N3—C3—C4—C5 | 0.1 (4) |
S2i—Zn1—N3—C3 | −106.29 (17) | C3i—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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S3ii | 0.89 (1) | 2.40 (1) | 3.280 (2) | 169 (2) |
Symmetry code: (ii) −x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C2HN2S3)2(C10H8N2)] |
Mr | 520.01 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 16.265 (5), 8.459 (3), 15.140 (5) |
β (°) | 94.459 (5) |
V (Å3) | 2076.8 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.80 |
Crystal size (mm) | 0.20 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.898, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5362, 1926, 1519 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.072, 1.02 |
No. of reflections | 1926 |
No. of parameters | 127 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.23, −0.32 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998) and SHELXTL (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL (Sheldrick, 1997).
Zn1—N3 | 2.061 (2) | S3—C1 | 1.677 (2) |
Zn1—S2 | 2.3204 (8) | N1—C1 | 1.332 (3) |
S1—C1 | 1.749 (2) | N1—N2 | 1.379 (3) |
S1—C2 | 1.758 (2) | N1—H1 | 0.892 (10) |
S2—C2 | 1.727 (2) | N2—C2 | 1.308 (3) |
N3—Zn1—N3i | 80.43 (13) | S2—Zn1—S2i | 117.86 (4) |
N3—Zn1—S2 | 106.31 (6) | C2—S2—Zn1 | 96.01 (8) |
N3i—Zn1—S2 | 120.49 (6) |
Symmetry code: (i) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S3ii | 0.892 (10) | 2.399 (11) | 3.280 (2) | 169 (2) |
Symmetry code: (ii) −x+1/2, −y+1/2, −z+1. |
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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).