Synthesis, Characterization, and Crystal Structures of Three New Divalent Metal Carboxylate-Sulfonates with a Layered and One-Dimensional Structure

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• 作者：Zhong-Ming Sun ; Jiang-Gao Mao ; Yan-Qiong Sun ; Hui-Yi Zeng ; and Abraham Clearfield
• 刊名：Inorganic Chemistry
• 出版年：2004
• 出版时间：January 12, 2004
• 年：2004
• 卷：43
• 期：1
• 页码：336 - 341
• 全文大小：250K
• 年卷期：v.43,no.1(January 12, 2004)
• ISSN：1520-510X

文摘

Hydrothermal reactions of 5-sulfoisophthalic acid (HO₃SC₆H₃-1,3-(CO₂H)₂, H₃L) with M(II) carbonate (or oxide) and4,4'-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 [Cd₃L₂(2,2-bipy)₄(H₂O)₂]·2H₂O (2) with layered structures and [ZnL(H-4,4'-bipy)(H₂O)]·2H₂O (3), whose structure features a one-dimensional double chain. The cadmium(II) ion in complex 1 isseven-coordinated by five carboxylate oxygen atoms and one sulfonate oxygen atom from four ligands and aunidentate 4,4'-bipyridine. The interconnection of the cadmium(II) ions through bridging carboxylate-sulfonate ligandsresulted 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 carboxylategroups from two ligands, a bidentate chelating 2,2'-bipy and an aqua ligand, and Cd(2) is octahedrally coordinatedby two bidentate chelating 2,2'-bipy's, a sulfonate oxygen, and an aqua ligand. The coordination geometry aroundCd(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 bridgingof 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(H₂O)] cations are orientated to the interlayer space. Complex 3features a 1D metal carboxylate-sulfonate double chain along the diagonal of the a- and b-axes. The zinc(II) ionis octahedrally coordinated by four carboxylate O atoms from three ligands, a unidentate 4,4'-bipy, and an aqualigand. Each pair of zinc(II) ions is bridged by two carboxylate groups from two ligands to form a dimer, and suchdimeric units are interconnected by bridging ligands to form a double chain. The sulfonate group of the carboxylatesulfonate ligand remains noncoordinated and forms a number of hydrogen bonds with aqua ligands as well aslattice water molecules.