Acta Cryst. (2009). E65, m838-m839 [ doi:10.1107/S160053680902371X ]
In the title compound, catena-poly[cadmium(II)-bis(![[mu]](/logos/entities/mu_rmgif.gif)
-5-amino-1,3,4-thiadiazole-2-thiolato)-![[kappa]](/logos/entities/kappa_rmgif.gif)
2N3:S2;2S2:N3], [Cd(C2H2N3S2)2]n, the CdII ion is coordinated by two N atoms of the 1,3,4-thiadiazole rings from two ligands and two S atoms of sulfhydryl from two other ligands in a slightly distorted tetrahedral geometry. The ligands bridge CdII ions, forming one-dimensional chains along [001], which are connected by N-H
N and N-HS hydrogen bonds into a three-dimensional network.
A mixture of 2-amino-5-mercapto-1,3,4-thiadiazole (39.95 mg, 0.3 mmol) (HL), LiOH.H2O (12.59 mg, 0.3 mmol) and Cd(NO3)2.4H2O (92.55 mg, 0.3 mmol) was dissolved in 25 ml MeOH/H2O. The resulting solution was filtered and the filtrate was allowed to stand for several days. Light yellow crystals were collected in about 30% yield (based on CdII).
H atoms of N were located in Fourier difference maps and refined with isotropic displacement parameters set at 1.2 times those of the parent N atoms.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./pk2170fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level for non-hydrogen atoms. Symmetry related atoms have the following symmetry codes: A = x, -y + 1, z + 1/2 B = -x + 1, -y + 1, -z AA= -x + 1, y, -z+1/2. |
![[Figure 2]](./pk2170fig2thm.gif)
| Fig. 2. The complexes are linked by N—H···N hydrogen bonds along the c axis. |
![[Figure 3]](./pk2170fig3thm.gif)
| Fig. 3. The complexes are connected by N—H···S hydrogen bonds along the a axis. |
| [Cd(C2H2N3S2)2] | F(000) = 728 |
| Mr = 376.77 | Dx = 2.368 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 2746 reflections |
| a = 12.6419 (11) Å | θ = 2.5–27.9° |
| b = 10.8341 (10) Å | µ = 2.83 mm−1 |
| c = 7.7241 (7) Å | T = 293 K |
| β = 92.795 (1)° | Block, colorless |
| V = 1056.66 (16) Å3 | 0.24 × 0.24 × 0.20 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 1232 independent reflections |
| Radiation source: fine-focus sealed tube | 1198 reflections with I > 2σ(I) |
| graphite | Rint = 0.015 |
| φ and ω scans | θmax = 27.9°, θmin = 2.5° |
| Absorption correction: multi-scan (SADABS ; Bruker, 1998) | h = −11→16 |
| Tmin = 0.550, Tmax = 0.602 | k = −14→14 |
| 3155 measured reflections | l = −10→10 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.015 | H-atom parameters constrained |
| wR(F2) = 0.043 | w = 1/[σ2(Fo2) + (0.0274P)2 + 0.7843P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max = 0.001 |
| 1232 reflections | Δρmax = 0.39 e Å−3 |
| 70 parameters | Δρmin = −0.49 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0116 (5) |
| [Cd(C2H2N3S2)2] | V = 1056.66 (16) Å3 |
| Mr = 376.77 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 12.6419 (11) Å | µ = 2.83 mm−1 |
| b = 10.8341 (10) Å | T = 293 K |
| c = 7.7241 (7) Å | 0.24 × 0.24 × 0.20 mm |
| β = 92.795 (1)° |
| Bruker SMART CCD area-detector diffractometer | 1232 independent reflections |
| Absorption correction: multi-scan (SADABS ; Bruker, 1998) | 1198 reflections with I > 2σ(I) |
| Tmin = 0.550, Tmax = 0.602 | Rint = 0.015 |
| 3155 measured reflections | θmax = 27.9° |
| R[F2 > 2σ(F2)] = 0.015 | H-atom parameters constrained |
| wR(F2) = 0.043 | Δρmax = 0.39 e Å−3 |
| S = 1.01 | Δρmin = −0.49 e Å−3 |
| 1232 reflections | Absolute structure: ? |
| 70 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 > 2σ(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 | ||
| Cd1 | 0.5000 | 0.582614 (14) | 0.2500 | 0.02585 (9) | |
| C1 | 0.62301 (13) | 0.34405 (15) | 0.0808 (2) | 0.0238 (3) | |
| C2 | 0.61171 (13) | 0.12413 (16) | 0.1243 (2) | 0.0267 (3) | |
| N1 | 0.56499 (11) | 0.28638 (13) | −0.03734 (18) | 0.0262 (3) | |
| N2 | 0.55650 (12) | 0.16022 (13) | −0.01418 (19) | 0.0289 (3) | |
| N3 | 0.61723 (13) | 0.00640 (15) | 0.1767 (2) | 0.0384 (4) | |
| H3A | 0.5834 | −0.0499 | 0.1182 | 0.046* | |
| H3B | 0.6546 | −0.0129 | 0.2687 | 0.046* | |
| S1 | 0.64750 (3) | 0.50104 (4) | 0.07269 (5) | 0.02700 (11) | |
| S2 | 0.67601 (4) | 0.24382 (4) | 0.23801 (6) | 0.03215 (12) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cd1 | 0.03358 (12) | 0.02365 (12) | 0.02017 (11) | 0.000 | −0.00030 (7) | 0.000 |
| C1 | 0.0249 (7) | 0.0262 (8) | 0.0202 (7) | 0.0030 (6) | −0.0006 (5) | 0.0004 (6) |
| C2 | 0.0242 (7) | 0.0278 (8) | 0.0282 (8) | 0.0013 (6) | 0.0016 (6) | 0.0024 (6) |
| N1 | 0.0326 (7) | 0.0236 (7) | 0.0219 (6) | −0.0002 (5) | −0.0033 (5) | −0.0001 (5) |
| N2 | 0.0349 (7) | 0.0234 (7) | 0.0281 (7) | 0.0002 (6) | −0.0027 (6) | 0.0004 (5) |
| N3 | 0.0346 (8) | 0.0297 (8) | 0.0500 (10) | −0.0012 (6) | −0.0079 (7) | 0.0144 (7) |
| S1 | 0.0292 (2) | 0.0257 (2) | 0.0261 (2) | −0.00241 (15) | 0.00115 (15) | −0.00137 (15) |
| S2 | 0.0341 (2) | 0.0325 (2) | 0.0287 (2) | −0.00058 (17) | −0.01070 (17) | 0.00401 (16) |
| Cd1—N1i | 2.2927 (14) | C2—N2 | 1.308 (2) |
| Cd1—N1ii | 2.2927 (14) | C2—N3 | 1.339 (2) |
| Cd1—S1 | 2.5264 (4) | C2—S2 | 1.7446 (18) |
| Cd1—S1iii | 2.5264 (4) | N1—N2 | 1.383 (2) |
| C1—N1 | 1.302 (2) | N1—Cd1ii | 2.2927 (14) |
| C1—S1 | 1.7304 (17) | N3—H3A | 0.8600 |
| C1—S2 | 1.7390 (16) | N3—H3B | 0.8600 |
| N1i—Cd1—N1ii | 103.50 (7) | N3—C2—S2 | 122.69 (13) |
| N1i—Cd1—S1 | 110.90 (4) | C1—N1—N2 | 115.35 (13) |
| N1ii—Cd1—S1 | 94.38 (4) | C1—N1—Cd1ii | 112.01 (11) |
| N1i—Cd1—S1iii | 94.38 (4) | N2—N1—Cd1ii | 132.61 (10) |
| N1ii—Cd1—S1iii | 110.90 (4) | C2—N2—N1 | 111.06 (15) |
| S1—Cd1—S1iii | 139.05 (2) | C2—N3—H3A | 120.0 |
| N1—C1—S1 | 122.83 (12) | C2—N3—H3B | 120.0 |
| N1—C1—S2 | 111.98 (12) | H3A—N3—H3B | 120.0 |
| S1—C1—S2 | 125.13 (9) | C1—S1—Cd1 | 100.73 (6) |
| N2—C2—N3 | 123.33 (17) | C1—S2—C2 | 87.62 (8) |
| N2—C2—S2 | 113.98 (13) | ||
| S1—C1—N1—N2 | 177.84 (12) | S2—C1—S1—Cd1 | −90.15 (11) |
| S2—C1—N1—N2 | 0.51 (19) | N1i—Cd1—S1—C1 | 128.77 (6) |
| S1—C1—N1—Cd1ii | −0.59 (17) | N1ii—Cd1—S1—C1 | −124.98 (6) |
| S2—C1—N1—Cd1ii | −177.93 (7) | S1iii—Cd1—S1—C1 | 4.38 (5) |
| N3—C2—N2—N1 | −179.98 (16) | N1—C1—S2—C2 | 0.11 (13) |
| S2—C2—N2—N1 | 1.14 (19) | S1—C1—S2—C2 | −177.15 (12) |
| C1—N1—N2—C2 | −1.1 (2) | N2—C2—S2—C1 | −0.74 (14) |
| Cd1ii—N1—N2—C2 | 176.95 (12) | N3—C2—S2—C1 | −179.63 (16) |
| N1—C1—S1—Cd1 | 92.87 (14) |
| Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1, −y+1, −z; (iii) −x+1, y, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···N2iv | 0.86 | 2.25 | 3.064 (2) | 158 |
| N3—H3B···N2v | 0.86 | 2.66 | 3.119 (2) | 114 |
| N3—H3B···S1vi | 0.86 | 2.74 | 3.4694 (17) | 144 |
| Symmetry codes: (iv) −x+1, −y, −z; (v) x, −y, z+1/2; (vi) −x+3/2, y−1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N3—H3A···N2i | 0.86 | 2.25 | 3.064 (2) | 158 |
| N3—H3B···N2ii | 0.86 | 2.66 | 3.119 (2) | 114 |
| N3—H3B···S1iii | 0.86 | 2.74 | 3.4694 (17) | 144 |
| Symmetry codes: (i) −x+1, −y, −z; (ii) x, −y, z+1/2; (iii) −x+3/2, y−1/2, −z+1/2. |
This work was supported by Beijing Municipal Natural Science Foundation (No. 2082004), the Innovation project for Doctors of Beijing University of Technology (bcx-2009-048) and the Seventh Technology Fund for Postgraduates of Beijing University of Technology (ykj-2009-2374).
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Owing to their potential as new functional materials, interest in self-assembled coordination polymeric complexes with versatile structure features has grown rapidly (Mulfort et al., 2007; Liu et al., 2003; Bauer et al., 2007). Hydrogen bonding is one highly directional supramolecular force, and although weaker than coordinative bonds, have been recognized to play critical roles in stabilizing and regulating the supramolecular construction (Dalrymple et al., 2007). Crystal engineering studies of hydrogen bonding in low-dimensional materials, especially in one-dimensional transition metal complexes, have been reported by several groups (Dong et al., 2006; Wang et al., 2005). Tzeng and coworkers have reported 2-amino-5-mercapto-1,3,4-thiadiazolate (L), acting as an auxiliary ligand and displaying its active coordination properties with Pd(II) (Tzeng, Lee et al., 2004) and Au(I) (Tzeng et al., 1999; Tzeng, Huang et al., 2004) to form diverse crystal structures. The various hydrogen bonding interactions have also been investigated, and have shown important effects in forming large molecular arrays. However, in these compounds, the ligand had unidentate coordination to metal ions with the sulfur atom of sulfhydryl. Herein, we report the crystal structure of CdII complex, [Cd(C2H2N3S2)2]n (I), using 2-amino-5-mercapto-1,3,4-thiadiazolate (L) as the unique bridging ligand and exhibiting one-dimensional chain structure feature.
A perspective view of a tetranuclear fragment of the chain is shown in Fig. 1. There is one crystallographically independent CdII ion coordinated to two nitrogen atoms which belong to the 1,3,4-thiadiazole rings from two ligands, with N1A—Cd1—N1B angle of 103.50 (7)°, two sulfur atoms of sulfhydryl from two other ligands with S1—Cd1—S1A angle of 139.05 (2)°, and displaying a slightly distorted tetrahedron geometry. The bond length of Cd—S is 2.5264 (4) Å, which is significantly longer than that of unidentate coordination to metal ions (Pd—S 2.2793 (9) Å, Tzeng, Lee et al., 2004) (Au—S 2.295 (5)–2.323 (4) Å, Tzeng et al., 1999; Tzeng, Huang et al., 2004). Nitrogen atoms participating in coordination may cause the Cd—S bond to lengthen. Simultaneously, each ligand bridges two CdII ions to from a one-dimensional chain along the c axis.
There are two kinds of hydrogen bond in the complex. N—H···N hydrogen bonds exist between the hydrogen atom of the amidogen from one chain and the uncoordinated nitrogen atom of the 1,3,4-thiadiazole ring from the adjacent chain. This joins the chains along the c axis into a two-dimensional plane (Fig. 2). N—H···S hydrogen bonds occur between the other hydrogen atom of the same amidogen and the sulfur atom of the coordinated sulfhydryl from an adjacent chain. This joins the one-dimensional chains along the a axis to create a two-dimensional plane (Fig. 3). The parameters of hydrogen bonds are given in the Table 1.