Synthesis and crystal structure of a new 1D Pb(II) coordination polymer containing salicylate and 2,2′-bipyridine ligands
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Wei-Wei Shi
Abstract
A new one-dimensional coordination polymer [Pb(2,2′-bipy)(Hsal)2]n has been synthesized and characterized by means of elemental analysis, FT-IR, powder X-ray diffraction, and X-ray single-crystal diffraction, where Hsal is salicylate, 2,2′-bipy is 2,2′-bipyridine. The compound consists of a one-dimensional chain, which was linked by C-H···π interactions and intermolecular C-H···O hydrogen bonds, therefore two-dimensional network was obtained.
The rational design and construction of metal-organic frameworks (MOFs) have received great interest due to their potential applications in many fields (Janiak, 2003; Della Rocca et al., 2011; Meek et al., 2011; Liu, 2012; Sava et al., 2012; Suh et al., 2012; Moon et al., 2013; Nugent et al., 2013), and based on the MOFs two-(2D) and three-(3D) dimensional networks (Kuang et al., 2011; Richards et al., 2012) can be easily formed. In our laboratory, MOFs were usually constructed by bridging ligands, such as 4-sulfobenzoate dianion (Zhang and Zhu, 2008a; Cheng et al., 2013), 4-aminobenzenesulfonate (Cheng et al., 2014), and 4,4′-bipyridine (Zhang and Zhu, 2006; Zhang and Zhu, 2008b). Now, we use salicylic acid as bridging ligand to synthesize MOFs. Salicylic acid (H2sal) with two functional groups (-COOH and -OH) displays a versatile ligand and exhibits different coordination modes (Devereux and Curran, 1996; Deacon et al., 2002; Thurston et al., 2002; Zhu and Cai, 2002). 2,2′-Bipyridine is often employed as a bidentate chelating ligand due to its good coordination ability with metal atoms along with its applications in constructing 2D and 3D dimensional architectures by means of non-covalent interactions such as hydrogen bonds and π-π stacking (Peppel et al., 2015; Thamilarasan et al., 2015). In order to synthesize novel complex, we introduced 2,2′-bipyridine into the system of PbII/H2sal. Finally, the new compound [Pb(2,2′-bipy)(Hsal)2]n was obtained. Here we report the preparation and structure of the complex.
Single-crystal X-ray diffraction reveals that compound crystallizes in the triclinic system, P-1 space group, and consists of one-dimensional (1D) coordination polymer of Pb(II). The adjacent Pb(II) atoms are bridged by two Hsal- ligands in tridentate chelating/bridging mode (Figure 1). Thus, all oxygens of carboxyl group from Hsal- ligand are interacting with lead (II) atoms. Pb(II) atom is coordinated by six O atoms from four Hsal- ligands and two N atoms of one 2,2′-bipyridine ligand (Figure 1) with the Pb(II) atom lying in an irregular eight coordinate [PbN2O6] environment, and the direction of Pb-N and Pb-O bonds shows that the coordination around the lead(II) atom in this complex is hemidirected (Shimoni-Livny et al., 1998; Janiak et al., 2000) (Figure 2). The observation in the shorter Pb-N and Pb-O (Table 1) bonds on the side of the lead(II) atom opposite to the position of the putative lone pair corroborates the presence of the stereo-active lone pair with a significant gap trans to the chelating 2,2′-bipyridine and Hsal- ligands (Figure 2). In the 1D coordination polymer chain, there are a number of Pb2O2 rings which was linked by Pb(II) atom and whose formula is [Pb(2,2′-bipy)(Hsal)2]n. The adjacent Pb2O2 rings are not parallel and the dihedral angle is 62.0(1)°. As listed in Table 1, Pb-O bond lengths are in the range of 2.451(4)–3.012(5) Å with four shorter and two longer, which are similar to the values in those reported complexes (Fan and Zhu, 2007; Zhang and Zhu, 2008a; Cheng et al., 2013). The Pb-N bond lengths [2.521(4) and 2.685(5) Å] (Table 1) are typical values and can be compared with those bonds in previously published PbII-complexes containing 2,2′-bipy ligand (Fan and Zhu, 2006; Zhang and Zhu, 2008a). Powder X-ray diffraction (PXRD) pattern of the complex was recorded and shown in Figure 3. The peak positions of experimental PXRD pattern are in agreement with the simulated powder pattern (Figure 4) for the complex calculated from the CIF by Mercury (Cambridge Crystallographic Data Centre, Cambridge, UK), but the strength of some peaks is somewhat changed.
The coordination environment of the Pb atom.
The hemidirected coordination environment of the Pb atom. Symmetry codes: (i) -x, 2-y, 1-z; (ii) 1-x, 2-y, 1-z.
Selected bond lengths (Å) and angles (deg) for the compound.
| Pb1-O1 | 2.535(4) |
| Pb1-O1i | 2.639(4) |
| Pb1-O2 | 3.012(5) |
| Pb1-O4 | 2.451(4) |
| Pb1-O5 | 2.793(4) |
| Pb1-O5ii | 2.948(4) |
| Pb1-N1 | 2.521(4) |
| Pb1-N2 | 2.685 (5) |
| O1-Pb1-O2 | 46.45(13) |
| O1-Pb1-O4 | 70.20(12) |
| O1-Pb1-O5 | 119.71(12) |
| O1-Pb1-N1 | 80.84(14) |
| O1-Pb1-N2 | 140.11(14) |
| O1-Pb1-O1i | 70.61(14) |
| O1-Pb1-O5ii | 132.60(12) |
| O2-Pb1-O4 | 68.80(15) |
| O2-Pb1-O5 | 102.00(12) |
| O2-Pb1-N1 | 123.34(15) |
| O2-Pb1-N2 | 173.28(14) |
| O2-Pb1-O1i | 98.83(12) |
| O2-Pb1-O5ii | 87.91(12) |
| O4-Pb1-O5 | 49.54(12) |
| O4-Pb1-N1 | 75.70(15) |
| O4-Pb1-N2 | 113.34(15) |
| O4-Pb1-O1i | 134.71(12) |
| O4-Pb1-O5ii | 109.50(12) |
| O5-Pb1-N1 | 85.49(14) |
| O5-Pb1-N2 | 76.04 (14) |
| O5-Pb1-O1i | 157.74(12) |
| O5-Pb1-O5ii | 75.25(12) |
| N1-Pb1-N2 | 63.16(15) |
| N1-Pb1-O1i | 76.52(13) |
| N1-Pb1-O5ii | 146.44(14) |
| N2-Pb1-O1i | 84.10(13) |
| N2-Pb1-O5ii | 85.37(14) |
| O1i-Pb1-O5ii | 113.48(12) |
Symmetry code: (i) -x, 2-y, 1-z; (ii) 1-x, 2-y, 1-z.
The powder X-ray pattern of the complex.
The simulated X-ray pattern of complex derived by Mercury from CIF.
In this complex, three kinds of non-covalent interactions are observed: (i) the uncoordinated O3/O6 atoms of Hsal- anion form strong intramolecular O-H···O hydrogen bonds with its O2/O4 (Figure 5, Table 2). In addition, two C-H···O hydrogen bonds (Figure 5, Table 2) are found between 2,2′-bipyridine and Hsal- ligands, one of them is intermolecular hydrogen-bonding interaction that links the adjacent polymer chains so that the 2D network was obtained; (ii) intermolecular C-H···π interaction (Janiak, 2000; Nishio, 2011), C10–H10···Cg1 (midpoint of the phenyl ring: C18i-C23i; symmetry code i: 1-x, 1-y, 1-z) with H···π distance (2.76 Å) and C-H···π angle (151°) is found between adjacent 1D chains in this crystal packing; (iii) there are π–π interactions between 2,2′-bipy and Hsal- ligands, with a centroid-to-centroid distance of 3.748(4) Å for rings N2/C6-C10 and C11ii–C16ii (symmetry code ii: -x, 2-y, 1-z). Therefore, the 1D polymer chain was not only stabilized by intramolecular hydrogen bonds and π–π interactions, but also extended into a 2D network by intermolecular hydrogen bonds and C-H···π interaction.
Hydrogen bonds as green dashed lines and C–H···π interactions as red dashed lines of the complex.
H-bonding geometry parameters (Å and deg) for the compound.
| Type | D-H···A | D-H (Å) | H···A (Å) | D···A (Å) | D-H···A (deg) |
|---|---|---|---|---|---|
| Intra- | O3-H3···O2 | 0.84 | 1.81 | 2.554(7) | 147 |
| Intra- | O6-H6···O4 | 0.84 | 1.81 | 2.550(7) | 146 |
| Intra- | C2-H2···O1 | 0.95 | 2.57 | 3.185(8) | 123 |
| Inter- | C4-H4···O2i | 0.95 | 2.48 | 3.338(9) | 151 |
Symmetry code: (i) x, -1+y, z.
Experimental
A mixture of Pb(NO3)2 (0.165 g, 0.5 mmol) (Sinopharm Chemical Reagent Co., Ltd, Shanghai, China) and 2,2′-bipy (0.5 mmol, 0.078 g) (Jinan Henghua Sci. & Tec. Co., Ltd, Jinan, China) in a dimethylformamide (10 mL)/water (20 mL) solution (Laiyang Fine Chemical Factory, Laiyang, China) was stirred for 5 min, and powdered salicylic acid (0.069 g, 0.5 mmol) (Tianjin Kemiou Chemical Reagent Co., Ltd, Tianjin, China) was added to the previous solution under stirring. The mixed solution was stirred for 2 h and filtered colorless block crystals were obtained after 2 months. All materials were commercially available and were of reagent grade. Yield: 48% based on a PbII salt. m.p.: 221°C–222°C. Anal. calcd. (%) for C24H18N2O6Pb: C, 45.21; H, 2.85; N, 4.39. Found (%): C, 45.33; H, 2.78; N, 4.37. IR (KBr, cm-1): 3447 s, 3422 s, 3067 m, 1624 m, 1591 s, 1551 m, 1485 s, 1466 s, 1438 m, 1377 s, 1339 m, 1302 m, 1250 m, 1225 w, 1172 w, 1144 w, 1059 w, 1030 w, 1010 m, 984 w, 862 m, 810 m, 773 s, 756 s, 743 s, 702 m, 669 m, 644 w, 536 w.
X-ray crystallography
Structure measurements was performed on a computer-controlled Bruker APEX-II CCD diffractometer (Bruker AXS, Karlsruhe, Germany) equipped with graphite-monochromated Mo-Ka radiation with radiation wavelength 0.71073 Å. Semi-empirical absorption correction was applied using SADABS program. The structure was solved by direct methods and refined with the full-matrix least-squares technique using the SHELXS-97 and SHELXL-97 programs (University of Göttingen, Göttingen, Germany) (Sheldrick, 1997). Computations on the non-covalent interactions were carried out with PLATON (Utrecht University, Utrecht, Netherlands) for Windows (Spek, 2008). The highest peak (2.84 e·Å-3) and lowest peak (-2.76 e·Å-3) in the final difference Fourier map for the complex are 0.91 Å and 0.95 Å from the Pb atom, respectively, indicating meaningless for atoms. Selected bond distances and angles are given in Table 1. Detailed crystal data and structure refinement is listed in Table 3. Crystallographic data have been deposited with the Cambridge Crystallographic Centre as supplementary publications number CCDC 977200.
Crystal data and refinement parameters.
| Empirical formula | C24H18N2O6Pb |
| Formula weight | 637.60 |
| Crystal dimensions(mm) | 0.16×0.17×0.18 |
| Crystal system | Triclinic |
| Space group | P-1 |
| a(Å) | 8.6886(17) |
| b(Å) | 10.096(2) |
| c(Å) | 13.197(3) |
| α(°) | 78.934(3) |
| β(°) | 89.122(3) |
| γ(°) | 70.883(2) |
| V(Å3) | 1071.7(4) |
| Z | 2 |
| Dc(g·cm-3) | 1.976 |
| μ(mm-1) | 7.917 |
| F(000) | 612 |
| T(K) | 173(2) |
| λ(Å) | MoKα(0.71073) |
| θ Range(°) | 1.57–25.01 |
| Measured reflections | 5450 |
| Unique reflections | 3719 |
| Observed reflections | 3517 |
| No. of parameters refined | 300 |
| R1,WR2[I>2σ(I)] | 0.0315,0.0841 |
| R1,WR2[all data] | 0.0331,0.0855 |
| GOOF | 1.059 |
| Largest peak and hole(e·Å-3) | 2.84, -2.76 |
Acknowledgments
We are grateful for the financial support from the National Natural Science Foundation of China (Grant No. 81201346), the Natural Science Foundation of Shandong Province (Grant No. ZR2014BL006), and A Project of Shandong Province Higher Educational Science and Technology Program (Grant No. J14LC19).
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Artikel in diesem Heft
- Frontmatter
- Research Articles
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- A low-temperature, environment-friendly approach to the synthesis of magnesium borates using magnesium waste scraps
- Short Communications
- Synthesis and crystal structure of a new 1D Pb(II) coordination polymer containing salicylate and 2,2′-bipyridine ligands
- Molecular structure of novel heterobimetallic thiolate [Cu(PPh3)]4(ZnCl)2(SEt)6.6THF
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Artikel in diesem Heft
- Frontmatter
- Research Articles
- Amino-functionalised metal xanthates
- The disilanes Cp*SiCl2SiH3 and Cp*SiH2SiH2Cp*
- Synthesis and characterization of gallium(III) dithiocarbamates as suitable nano-gallium(III) sulfide precursors
- Synthesis, structure and in vitro cytotoxic activity of two organotin complexes of 2-phenyl-1,2, 3-triazole-4-carboxylic acid
- Synthesis and structure of [2-((L)-menthoxycarbonyl)ethyl]diphenyltin halides
- A low-temperature, environment-friendly approach to the synthesis of magnesium borates using magnesium waste scraps
- Short Communications
- Synthesis and crystal structure of a new 1D Pb(II) coordination polymer containing salicylate and 2,2′-bipyridine ligands
- Molecular structure of novel heterobimetallic thiolate [Cu(PPh3)]4(ZnCl)2(SEt)6.6THF
- Mercury(I) chloride in vivo oxidation: a thermodynamic study
