Sun Zhong-Ming, Mao Jiang-Gao, Sun Yan-Qiong, Zeng Hui-Yi, Clearfield Abraham
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, PR China.
Inorg Chem. 2004 Jan 12;43(1):336-41. doi: 10.1021/ic0343307.
Hydrothermal reactions of 5-sulfoisophthalic acid (HO(3)SC(6)H(3)-1,3-(CO(2)H)(2), H(3)L) with M(II) carbonate (or oxide) and 4,4'-bipyridine (4,4'-bipy) (or 2,2'-bipyridine, 2,2'-bipy) resulted in three new metal carboxylate-sulfonate hybrids, namely, [CdL(H-4,4'-bipy)] (1) and [Cd(3)L(2)(2,2-bipy)(4)(H(2)O)(2)].2H(2)O (2) with layered structures and [ZnL(H-4,4'-bipy)(H(2)O)].2H(2)O (3), whose structure features a one-dimensional double chain. The cadmium(II) ion in complex 1 is seven-coordinated by five carboxylate oxygen atoms and one sulfonate oxygen atom from four ligands and a unidentate 4,4'-bipyridine. The interconnection of the cadmium(II) ions through bridging carboxylate-sulfonate ligands resulted in the formation of a <002> double layer with the bipyridyl rings orientated toward the interlayer space. Complex 2 has a different layered structure. Cd(1) is seven-coordinated by two bidentate chelating carboxylate groups from two ligands, a bidentate chelating 2,2'-bipy and an aqua ligand, and Cd(2) is octahedrally coordinated by two bidentate chelating 2,2'-bipy's, a sulfonate oxygen, and an aqua ligand. The coordination geometry around Cd(3) is similar to that of Cd(1) with the aqua ligand being replaced by an oxygen atom from the sulfonate group. The carboxylate-sulfonate ligand acts as pentadentate ligand, bridging with three cadmium(II) ions. The bridging of cadmium(II) ions through the carboxylate-sulfonate ligands resulted in the formation of <006> and <003> layers; the 2,2'-bipy molecules and [Cd(2)(2,2'-bipy)(2)(H(2)O)] cations are orientated to the interlayer space. Complex 3 features a 1D metal carboxylate-sulfonate double chain along the diagonal of the a- and b-axes. The zinc(II) ion is octahedrally coordinated by four carboxylate O atoms from three ligands, a unidentate 4,4'-bipy, and an aqua ligand. Each pair of zinc(II) ions is bridged by two carboxylate groups from two ligands to form a dimer, and such dimeric units are interconnected by bridging ligands to form a double chain. The sulfonate group of the carboxylate sulfonate ligand remains noncoordinated and forms a number of hydrogen bonds with aqua ligands as well as lattice water molecules.
5-磺基间苯二甲酸（HO(3)SC(6)H(3)-1,3-(CO(2)H)(2)，H(3)L）与M(II)碳酸盐（或氧化物）以及4,4'-联吡啶（4,4'-bipy）（或2,2'-联吡啶，2,2'-bipy）发生水热反应，得到了三种新型金属羧酸盐-磺酸盐杂化物，即具有层状结构的[CdL(H-4,4'-bipy)]（1）和[Cd(3)L(2)(2,2-bipy)(4)(H(2)O)(2)].2H(2)O（2）以及结构具有一维双链的[ZnL(H-4,4'-bipy)(H(2)O)].2H(2)O（3）。配合物1中的镉(II)离子由来自四个配体的五个羧酸盐氧原子、一个磺酸盐氧原子以及一个单齿的4,4'-联吡啶七配位。镉(II)离子通过桥连羧酸盐-磺酸盐配体相互连接，形成了一个<002>双层结构，联吡啶环朝向层间空间。配合物2具有不同的层状结构。Cd(1)由来自两个配体的两个双齿螯合羧酸盐基团、一个双齿螯合的2,2'-bipy和一个水合配体七配位，Cd(2)由两个双齿螯合的2,2'-bipy、一个磺酸盐氧原子和一个水合配体八面体配位。Cd(3)周围的配位几何结构与Cd(1)相似，水合配体被磺酸盐基团的一个氧原子取代。羧酸盐-磺酸盐配体作为五齿配体，与三个镉(II)离子桥连。镉(II)离子通过羧酸盐-磺酸盐配体桥连形成了<006>和<003>层；2,2'-bipy分子和[Cd(2)(2,2'-bipy)(2)(H(2)O)]阳离子朝向层间空间。配合物3沿a轴和b轴的对角线方向具有一维金属羧酸盐-磺酸盐双链结构。锌(II)离子由来自三个配体的四个羧酸盐O原子、一个单齿的4,4'-bipy和一个水合配体八面体配位。每对锌(II)离子由来自两个配体的两个羧酸盐基团桥连形成二聚体，并且这些二聚体单元通过桥连配体相互连接形成双链。羧酸盐磺酸盐配体的磺酸盐基团保持未配位状态，并与水合配体以及晶格水分子形成大量氢键。
