Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041797/ci2441sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041797/ci2441Isup2.hkl |
CCDC reference: 660174
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (N-C) = 0.002 Å
- R factor = 0.019
- wR factor = 0.047
- Data-to-parameter ratio = 17.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.72 PLAT322_ALERT_2_C Check Hybridisation of S1 in Main Residue . ?
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 0.723 Tmax scaled 0.723 Tmin scaled 0.623 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) 2.01 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 2 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 1 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 literature, see: Bats (1976); Li et al. (2005); Ma et al. (2004a, 2004b); Mura et al. (1985); Qiu et al. (2006); Tannai et al. (2003, 2005, 2006); Tzeng et al. (2007).
The title compound was synthesized by the hydrothermal method. A mixture of ZnCl2 (27 mg, 0.2 mmol) and 2,5-dimercapto-1,3,4-thiodiazole (60 mg, 0.4 mmol) in water (10 ml) was placed in a Teflon-lined stainless-steel Parr bomb. The bomb was heated at 413 K for 30 h and then allowed to cool to room temperature; colourless crystals were isolated in about 20% yield. FT—IR (KBr pellets, cm-1): 3157m, 1593w, 1478 s, 1411m, 1297m, 1124 s, 1103 s, 1036 s, 734m, 668w, 581w, 544m.
Atom H1 was located in a difference map and refined isotropically, with an N—H distance restraint of 0.90 (1) Å.
The structures of free 2,5-dimercapto-1,3,4-thiodiazole (Bats, 1976) and some of its metal-complexes (Li et al., 2005; Mura et al., 1985; Ma et al., 2004a,b; Qiu et al., 2006; Tannai et al., 2003, 2005, 2006; Tzeng et al., 2007) have been reported. In such complexes, the 2,5-dimercapto-1,3,4-thiodiazole ligand shows different valences and different coordination modes. Herein, we report a neutral ZnII complex, [Zn(C2HN2S3)2]n, with the above ligand.
As shown in Fig. 1, the ZnII atom lies at a site of 2 symmetry. It is four-coordinated by four symmetry related 5-thioxo-1H-1,2,4-thiadiazole-3-thiolate ligands through their S atoms to form a tetrahedral geometry. The S—Zn distances are 2.3343 (6) and 2.3560 (6) Å, and S—Zn—S angles range from 103.78 (3) to 112.572 (17)° (Table 1). Each of the ligand coordinates to two ZnII atoms through the two terminal S atoms to form a chiral two-dimensional layer (Fig. 2) containing homochiral helical chains (left- or right-hand single helical chain). The separation of ZnII atom across the ligand is 7.779 (6) Å and the screw-pitch is 7.604 (5) Å. However, in the crystal structure, adjacent layers have opposite chirality, and were connected into a three-dimensional network by N—H···S hydrogen bonds (see Table 2).
For related literature, see: Bats (1976); Li et al. (2005); Ma et al. (2004a, 2004b); Mura et al. (1985); Qiu et al. (2006); Tannai et al. (2003, 2005, 2006); Tzeng et al. (2007).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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: SHELXL97.
[Zn(C2HN2S3)2] | F(000) = 720 |
Mr = 363.83 | Dx = 2.138 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 9116 reflections |
a = 12.983 (3) Å | θ = 3.1–27.5° |
b = 11.448 (2) Å | µ = 3.25 mm−1 |
c = 7.6035 (15) Å | T = 293 K |
V = 1130.1 (4) Å3 | Block, colourless |
Z = 4 | 0.20 × 0.12 × 0.10 mm |
Bruker SMART 1000 CCD area-detector diffractometer | 1298 independent reflections |
Radiation source: fine-focus sealed tube | 1213 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
φ and ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −16→16 |
Tmin = 0.863, Tmax = 1.000 | k = −14→14 |
10211 measured reflections | l = −8→9 |
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)] = 0.019 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0201P)2 + 0.66P] where P = (Fo2 + 2Fc2)/3 |
1298 reflections | (Δ/σ)max = 0.001 |
73 parameters | Δρmax = 0.34 e Å−3 |
1 restraint | Δρmin = −0.32 e Å−3 |
[Zn(C2HN2S3)2] | V = 1130.1 (4) Å3 |
Mr = 363.83 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 12.983 (3) Å | µ = 3.25 mm−1 |
b = 11.448 (2) Å | T = 293 K |
c = 7.6035 (15) Å | 0.20 × 0.12 × 0.10 mm |
Bruker SMART 1000 CCD area-detector diffractometer | 1298 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 1213 reflections with I > 2σ(I) |
Tmin = 0.863, Tmax = 1.000 | Rint = 0.030 |
10211 measured reflections |
R[F2 > 2σ(F2)] = 0.019 | 1 restraint |
wR(F2) = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.34 e Å−3 |
1298 reflections | Δρmin = −0.32 e Å−3 |
73 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 | 0.16347 (3) | 0.2500 | 0.02437 (9) | |
S2 | 0.47751 (3) | 0.28669 (5) | 0.00481 (7) | 0.03425 (13) | |
S1 | 0.64938 (3) | 0.44469 (4) | −0.11880 (7) | 0.03453 (13) | |
S3 | 0.85977 (3) | 0.46238 (4) | −0.28194 (6) | 0.02663 (11) | |
N1 | 0.66827 (11) | 0.23028 (13) | −0.1150 (2) | 0.0291 (3) | |
N5 | 0.76058 (11) | 0.26501 (13) | −0.1854 (2) | 0.0297 (3) | |
C2 | 0.76163 (12) | 0.37822 (15) | −0.1961 (2) | 0.0223 (3) | |
C1 | 0.59931 (13) | 0.30944 (15) | −0.0721 (2) | 0.0248 (3) | |
H1 | 0.6565 (19) | 0.1542 (9) | −0.109 (4) | 0.058 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.02160 (14) | 0.02878 (16) | 0.02272 (15) | 0.000 | −0.00047 (10) | 0.000 |
S2 | 0.0217 (2) | 0.0482 (3) | 0.0329 (3) | 0.00767 (18) | 0.00397 (18) | 0.0153 (2) |
S1 | 0.0295 (2) | 0.0264 (2) | 0.0477 (3) | 0.00416 (17) | 0.0111 (2) | −0.00510 (19) |
S3 | 0.0236 (2) | 0.0240 (2) | 0.0323 (2) | 0.00054 (15) | 0.00432 (17) | 0.00029 (16) |
N1 | 0.0241 (7) | 0.0247 (7) | 0.0386 (8) | 0.0021 (6) | 0.0049 (6) | 0.0062 (6) |
N5 | 0.0232 (7) | 0.0263 (8) | 0.0395 (8) | 0.0037 (6) | 0.0069 (7) | 0.0030 (6) |
C2 | 0.0201 (7) | 0.0256 (8) | 0.0211 (7) | 0.0029 (6) | 0.0005 (6) | −0.0027 (6) |
C1 | 0.0239 (8) | 0.0303 (8) | 0.0203 (8) | 0.0023 (6) | −0.0010 (6) | 0.0037 (6) |
Zn1—S3i | 2.3343 (6) | S3—C2 | 1.7258 (17) |
Zn1—S3ii | 2.3343 (6) | S3—Zn1iv | 2.3343 (6) |
Zn1—S2iii | 2.3560 (6) | N1—C1 | 1.315 (2) |
Zn1—S2 | 2.3560 (6) | N1—N5 | 1.371 (2) |
S2—C1 | 1.7060 (17) | N1—H1 | 0.885 (10) |
S1—C1 | 1.7164 (18) | N5—C2 | 1.299 (2) |
S1—C2 | 1.7458 (16) | ||
S3i—Zn1—S3ii | 103.78 (3) | C1—N1—H1 | 123.2 (17) |
S3i—Zn1—S2iii | 112.572 (17) | N5—N1—H1 | 117.1 (17) |
S3ii—Zn1—S2iii | 110.807 (17) | C2—N5—N1 | 108.84 (14) |
S3i—Zn1—S2 | 110.807 (18) | N5—C2—S3 | 126.06 (12) |
S3ii—Zn1—S2 | 112.572 (17) | N5—C2—S1 | 113.90 (12) |
S2iii—Zn1—S2 | 106.44 (3) | S3—C2—S1 | 120.02 (10) |
C1—S2—Zn1 | 104.35 (6) | N1—C1—S2 | 127.66 (14) |
C1—S1—C2 | 89.58 (8) | N1—C1—S1 | 108.20 (12) |
C2—S3—Zn1iv | 101.07 (6) | S2—C1—S1 | 124.04 (10) |
C1—N1—N5 | 119.47 (15) | ||
S3i—Zn1—S2—C1 | −147.61 (7) | C1—S1—C2—N5 | −0.51 (14) |
S3ii—Zn1—S2—C1 | −31.90 (7) | C1—S1—C2—S3 | 177.92 (11) |
S2iii—Zn1—S2—C1 | 89.68 (7) | N5—N1—C1—S2 | 175.91 (13) |
C1—N1—N5—C2 | 0.2 (2) | N5—N1—C1—S1 | −0.5 (2) |
N1—N5—C2—S3 | −178.01 (13) | Zn1—S2—C1—N1 | 53.89 (17) |
N1—N5—C2—S1 | 0.31 (19) | Zn1—S2—C1—S1 | −130.19 (10) |
Zn1iv—S3—C2—N5 | −23.57 (17) | C2—S1—C1—N1 | 0.55 (13) |
Zn1iv—S3—C2—S1 | 158.20 (8) | C2—S1—C1—S2 | −176.05 (12) |
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) −x+3/2, −y+1/2, z+1/2; (iii) −x+1, y, −z+1/2; (iv) −x+3/2, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S3v | 0.89 (1) | 2.57 (2) | 3.339 (2) | 146 (2) |
N1—H1···S3ii | 0.89 (1) | 2.83 (2) | 3.378 (2) | 121 (2) |
Symmetry codes: (ii) −x+3/2, −y+1/2, z+1/2; (v) −x+3/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C2HN2S3)2] |
Mr | 363.83 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 293 |
a, b, c (Å) | 12.983 (3), 11.448 (2), 7.6035 (15) |
V (Å3) | 1130.1 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.25 |
Crystal size (mm) | 0.20 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.863, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10211, 1298, 1213 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.047, 1.08 |
No. of reflections | 1298 |
No. of parameters | 73 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.32 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXL97.
Zn1—S3i | 2.3343 (6) | Zn1—S2 | 2.3560 (6) |
S3ii—Zn1—S3i | 103.78 (3) | S3i—Zn1—S2 | 112.572 (17) |
S3ii—Zn1—S2 | 110.807 (18) | S2iii—Zn1—S2 | 106.44 (3) |
Symmetry codes: (i) −x+3/2, −y+1/2, z+1/2; (ii) x−1/2, −y+1/2, −z; (iii) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S3iv | 0.89 (1) | 2.57 (2) | 3.339 (2) | 146 (2) |
N1—H1···S3i | 0.89 (1) | 2.83 (2) | 3.378 (2) | 121 (2) |
Symmetry codes: (i) −x+3/2, −y+1/2, z+1/2; (iv) −x+3/2, y−1/2, z. |
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- If you have already subscribed, you may need to register
The structures of free 2,5-dimercapto-1,3,4-thiodiazole (Bats, 1976) and some of its metal-complexes (Li et al., 2005; Mura et al., 1985; Ma et al., 2004a,b; Qiu et al., 2006; Tannai et al., 2003, 2005, 2006; Tzeng et al., 2007) have been reported. In such complexes, the 2,5-dimercapto-1,3,4-thiodiazole ligand shows different valences and different coordination modes. Herein, we report a neutral ZnII complex, [Zn(C2HN2S3)2]n, with the above ligand.
As shown in Fig. 1, the ZnII atom lies at a site of 2 symmetry. It is four-coordinated by four symmetry related 5-thioxo-1H-1,2,4-thiadiazole-3-thiolate ligands through their S atoms to form a tetrahedral geometry. The S—Zn distances are 2.3343 (6) and 2.3560 (6) Å, and S—Zn—S angles range from 103.78 (3) to 112.572 (17)° (Table 1). Each of the ligand coordinates to two ZnII atoms through the two terminal S atoms to form a chiral two-dimensional layer (Fig. 2) containing homochiral helical chains (left- or right-hand single helical chain). The separation of ZnII atom across the ligand is 7.779 (6) Å and the screw-pitch is 7.604 (5) Å. However, in the crystal structure, adjacent layers have opposite chirality, and were connected into a three-dimensional network by N—H···S hydrogen bonds (see Table 2).