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Main Group Metal Chemistry

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Volume 36, Issue 3-4


Synthesis, characterization, and crystal structure of catena-poly[bis(carboxybenzenesulfonato)-bis(1,10-phenanthroline)lead(II)0.5(4,4′-bipy)]

Yuan-Zheng Cheng / Xin-Tong Zhao / Ying Tang
  • Affiliated Hospital of Weifang Medical University, Weifang Medical University, Weifang 261053, China
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Wei-Wei Shi / Li-Ping Zhang
Published Online: 2013-07-05 | DOI: https://doi.org/10.1515/mgmc-2013-0018


A new lead complex, {[Pb(4-sb)(phen)](4,4′-bipy)0.5}n (1) (where 4-sb=4-sulfobenzoate dianion, phen=1,10-phenanthroline, 4,4′-bipy=4,4′-bipyridine), was synthesized and characterized by single-crystal X-ray, infrared, and thermogravimetric analyses and fluorescence studies. In this compound, the lead atom is hexacoordinated by two N atoms of one phen ligand and four O atoms from three 4-sb dianions. Each 4-sb serves as a bridging ligand, connecting adjacent PbII atoms into a centrosymmetric polymeric chain. Intermolecular π-π interactions and hydrogen bonds are observed in the complex, which stabilize the crystal packing and give rise to three-dimensional architecture.

Keywords: coordination polymer; 4-sulfobenzoate; lead(II); X-ray


Coordination polymers (also called metal-organic frameworks) are a type of supramolecular complexes containing metal ions linked together by organic bridging ligands (Janiak, 1997, 2003), which have attracted great interest in recent years owing to their potential applications in magnetism, catalysis, gas storage, fluorescence, and gas separation (Janiak and Vieth, 2010; Stylianou et al., 2010; Bloch et al., 2012; Harding and Reynolds, 2012; Hwang et al., 2012; Zheng et al., 2012). Moreover, the design and synthesis of complexes containing two or more neutral amine ligands continue to be a very active research field because of their applications in constructing a variety of supramolecular complexes (Bonnet et al., 2003; Schmittel et al., 2009). 4-Sulfobenzoate dianion (4-sb) has two functional groups (-SO3- and -COO-), which can be used as bridging ligand to construct metal-organic frameworks and whose oxygen atoms can be used as H-bonding acceptor to form hydrogen bonds (Zhang and Zhu, 2006). The Pb(II) atom with a 4f145d106s2 electronic configuration can perform flexible coordination modes (Ying and Mao, 2004; Zhang et al., 2005a,b; Miao and Zhu, 2008; Zhang and Zhu, 2008a; Jin et al., 2010) and is able to bind to various ligands. In the past decades, 1,10-phenanthroline (phen) is frequently used as a chelating ligand not only because of its good ability to coordinate with metal atoms but also because of its applications in generating supramolecular structure by noncovalent interactions such as π-π stacking and hydrogen bonds (Accorsi et al., 2009; Visinescu et al., 2013). A similar situation occurs in 4,4′-bipyridine (4,4′-bipy), which is also widely used in synthesizing supramolecular complexes due to its flexible coordination modes or existing forms. In previous reported complexes (Zhang and Zhu, 2008b; Shi et al., 2010; Li et al., 2012), 4,4′-bipy served as bidentate ligand, monodentate ligand, and guest molecule. In addition, 4,4′-bipy also can generate hydrogen bonds (Zhang and Zhu, 2006). Therefore, in order to obtain new and stable supramolecular coordination complex polymers, two neutral amine ligands (phen and 4,4′-bipy) were used in the system PbII/4-sb, and a new coordination polymer, {[Pb(4-sb)(phen)](4,4′-bipy)0.5}n (1), was obtained.

Results and discussion


In this complex, the 4-sb is a bridging ligand. Four coordination polymers containing PbII atom and 4-sb ligand had been synthesized when 4-sb dianion acted as a bridging ligand (Zhang et al., 2005a,b; Zhang and Zhu, 2008a). In these four complexes, one has no neutral amine ligand; the others contain one neutral amine ligand. In order to construct a novel and supramolecular coordination polymer, we introduced two neutral amine ligands into the system of PbII/4-sb. The compound was synthesized by the reaction of Pb(NO3)2, 4-sb, phen, 4,4′-bipy, dimethyformamide (DMF), and water under reflux, in which 4,4′-bipy does not coordinate to PbII ion and acts as a guest molecule. It is worth noting that π-π interactions between 4,4′-bipy and phen stabilize the three-dimensional (3D) network.

Infrared spectral studies

In the infrared (IR) spectra of the complex there is no absorption near 1700 cm-1, indicating that COOH is deprotonated. The νas(COO-) and νs(COO-) are at 1598 and 1386 cm-1, respectively, indicating that the COO- group is a chelating ligand. The characteristic vibrations of νas(SO3-) in the complex are at 1207, 1180, and 1114 cm-1, whereas the vs(SO3-) absorption is at 1037 cm-1.

Structure analysis

The structure of the complex was determined by single-crystal X-ray crystallography. The complex consists of a 1D ladderlike chain, constructed from PbII ions, phen, and 4-sb ligands, whereas the 4,4′-bipy acts as a guest molecule in the crystal packing (Figure 1). Each PbII ion is six-coordinated by two N atoms from one phen ligand and four O atoms: two O atoms from one carboxyl group and another two O atoms from two sulfonyl groups of two different 4-sb ligands. The 4-sb ligand coordinates to PbII ion by η43 mode with Pb1-O bond lengths between 2.355(2) and 3.034(2) Å (Table 1). The bond lengths of Pb1-O (COO-) are 2.355(2) and 2.751(2) Å, which are comparable to those in the reported compound [Pb(C12H8N2)(C7H4O5S)]n·nH2O [2.439(3) and 2.888(3) Å] (Zhang et al., 2005b). The Pb-O (SO3-) bonds have one shorter distance [2.670(2) Å] and one longer distance [3.034(2) Å], which are in normal range and can be found in previous articles (Miao and Zhu, 2008; Zhang and Zhu, 2008a). The Pb1-N distances are 2.503(2) and 2.534(2) Å (Table 1), which are similar to those found in [Pb(2-Hstp)(o-phen)] [2.509(5) and 2.528(5) Å] (Ren et al., 2011). However, they are slightly less than the Pb1-N bond lengths [2.540 (4) and 2.546(4) Å] in [Pb(C12H8N2)(C7H4O5S)]n·nH2O (Zhang et al., 2005b). The distances of Pb…Pb separated by the 4-sb ligands are 10.1966(18) and 12.5316(17) Å, whereas the Pb…Pb separation by sulfonates is 6.2173(9) Å.

Coordination environment of the Pb atom with 4,4′-bipy acting as a guest molecule.
Figure 1

Coordination environment of the Pb atom with 4,4′-bipy acting as a guest molecule.

Table 1

Selected bond lengths (Å) and angles (deg) for the title compound.

Lead complex geometries can be classified as holodirected and hemidirected (Janiak et al., 2000). In this compound, an obvious gap can be found in a site opposite to the position of the phen ligand (Figure 2). In addition, Pb1-O bond distances range from 2.355(2) to 3.034(2) Å, which are largely different. Therefore, the Pb(II) atom adopted hemidirected coordination geometry, and the lone pair of electrons on Pb(II) atom is stereochemically active.

Geometry of the Pb atom.
Figure 2

Geometry of the Pb atom.

In the crystal, there are two kinds of π-π stacking interactions (Janiak, 2000) between neighboring aromatic molecules (Figure 3 and Table 2): One occurs between neighboring phen ligands by partial overlap of rings Cg1 (N1/C1–C5) and Cg1 (N1i/C1i–C5i) [symmetry code (i): 1-x, 1-y, 2-z], and the dihedral angle between them is 0°. The perpendicular plane-to-plane distance between the two rings is 3.1757(12) Å, and the centroid-to-centroid distance is 3.4289(19) Å. Another occurs between phen and 4,4′-bipy with the centroid-to-centroid distances ranging from 3.507(2) to 3.761(2) Å. Weak hydrogen bonds (C-H…O bonding) between phen and oxygen atoms of 4-sb ligands are observed (Figure 4 and Table 3). The 3D architecture was generated by π-π stacking interactions and hydrogen bonds, and what’s more, the π-π interactions between phen and 4,4′-bipy make the 3D network more stable.

The π-π stacking of the title compound.
Figure 3

The π-π stacking of the title compound.

Table 2

The π-π stacking interactions of the title compound.

Hydrogen bonding (green dashed lines) in the complex.
Figure 4

Hydrogen bonding (green dashed lines) in the complex.

Table 3

H-bonding geometry parameters (Å and deg) for the title compound.

Thermal stability behavior

Thermogravimetric analysis (TGA) was performed on the compound by heating the compound to 600°C. TGA for the complex showed that 4,4′-bipy was partly lost between 202°C and 205°C (observed, 0.59%), followed by the further loss of 4,4′-bipy in the range 297–327°C (observed 10.53%). The sum of weight loss in the range 202–327°C is 11.12%, which corresponds to the removal of 0.5 4,4′-bipy molecule (calculated, 11.73%). One phenanthroline ligand was lost in the range 329–408°C (calculated, 27.07%; observed, 26.32%). The complex further lost mass between 437°C and 550°C, probably corresponding to the release of part 4-sb ligand. Finally, the remaining mass of 46.46% is presumably PbSO4 (calculated, 45.56%).

Fluorescence property

The photoluminescent behaviors of the complex as well as the free ligands are researched in solid state at room temperature. The peak of the complex at 457 nm (λex=214 nm), which is similar to the peak of 4,4′-bipy [456 nm (λex=216 nm)] and the peak of 4-sb [457 nm (λex=217 nm)]. So the emissions come from 4,4′-bipy and 4-sb ligands and are probably neither metal-to-ligand nor ligand-to-metal charge transfer.


{[Pb(4-sb)(phen)](4,4′-bipy)0.5}n has been prepared and characterized by single-crystal X-ray analyses, IR, TGA, and fluorescence studies. In summary, the compound was synthesized by the reaction of PbII ions, 4-sb, phen ligands, and 4,4′-bipy molecules. 4-Sb serves as a bridging ligand, connecting adjacent PbII atoms into a centrosymmetric polymeric chain. Aromatic-aromatic stacking interactions occur between neighboring amine ligands. Weak hydrogen bonds are also found in the compound. On the basis of the weak interactions, the compound is extended into 3D supramolecular network.



All materials were commercially available and were of reagent grade. Fourier transform IR (FTIR) spectra were recorded on an IR Affinity-1 FTIR spectrophotometer (Shimadzu Corporation, Kyoto, Japan) (range, 400–4000 cm-1) as KBr pellets. TGA was studied with a Mettler 5MP/PF7548/MET/400W instrument (Mettler Toledo Company, Zurich, Switzerland) in a N2 atmosphere in the temperature range between 25°C and 600°C (heating rate=10°C/min). Fluorescence spectra were recorded on a Varian Cary Eclipse fluorescence spectrometer (Varian, Inc., Palo Alto, CA, USA) in the solid state at room temperature. Crystal structure was determined on a Bruker SMART APEX II CCD X-ray diffractometer (Bruker AXS, Karlsruhe, Germany).

Preparation of {[Pb(4-sb)(phen)] (4,4′-bipy)0.5}n

A mixture of Pb(NO3)2 (0.165 g, 0.5 mmol), 4-sulfobenzoic acid monopotassium salt (0.120 g, 0.5 mmol), 4,4′-bipy (0.156 g, 1.0 mmol), and phen (0.198 g, 0.1 mmol) in a water/DMF (3:1) solution (20 mL ) was refluxed for 10 h and filtered. Yellow block crystals were obtained after about 1 month. Yield: 10.4% based on a phen ligand.

X-ray crystallography

Single-crystal X-ray diffraction analysis was carried out with a Bruker SMART APEX II CCD X-ray diffractometer at room temperature using graphite monochromated MoKα radiation (λ=0.71073 Å). All data were corrected for absorption by use of the SADABS program (Sheldrick, 1997a). The structures were solved by direct methods using the SHELXS-97 program (Sheldrick, 1997b). Full-matrix least-squares refinements on F2 were carried out using the SHELXL-97 package (Sheldrick, 1997c). Selected bond distances and angles are given in Table 1. Detailed crystal data and structure refinement are listed in Table 4. Crystallographic data have been deposited with the Cambridge Crystallographic Centre as supplementary publication number CCDC-854050.

Table 4

Crystal data and refinement parameters.

The authors thank the National Natural Science Foundation of China (grant 81201346/H2004) and financial support from Shandong Provincial Education Department (grant no. J09LB57).


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About the article

Corresponding author: Li-Ping Zhang, Department of Chemistry, Weifang Medical University, Weifang 261053, China

Received: 2013-03-24

Accepted: 2013-06-05

Published Online: 2013-07-05

Published in Print: 2013-07-01

Citation Information: Main Group Metal Chemistry, Volume 36, Issue 3-4, Pages 117–122, ISSN (Online) 2191-0219, ISSN (Print) 0792-1241, DOI: https://doi.org/10.1515/mgmc-2013-0018.

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