Two Novel Flexible Multidentate Ligands for Crystal Engineering: Syntheses, Structures, and Properties of Cu II , Mn II Complexes with N ‐[(3‐Carboxyphenyl)sulfonyl]glycine and N , N′ ‐(1,3‐Phenylenedisulfonyl)bis(glycine)

One novel N ‐[(3‐carboxyphenyl)sulfonyl]glycine (H 3 L 1 ) ligand ( 1 ) was prepared in high yield, and its structure was determined by single‐crystal X‐ray diffraction. Reaction of H 3 L 1 with Mn(ClO 4 ) 2 · 6H 2 O at different pH values gave two new dinuclear complexes: [Mn 2 (HL 1 ) 2 (phen) 4 ] · 16H 2 O ( 2 ) and [Mn 2 L 1 (phen) 4 (H 2 O)]ClO 4 · 3H 2 O ( 3 ) (phen = 1,10‐phenanthroline). Additionally, two copper(II) complexes, [K 2 Cu(L 2 ) 2 (H 2 O) 2 ] n ( 4 ) and [CuL 2 (H 2 O)] 2 · 2H 2 O ( 5 ), involving another novel ligand, N , N′ ‐(1,3‐phenylenedisulfonyl)bis(glycine) (H 2 L 2 ), were prepared by a one‐pot reaction of 1,3‐phenylenebis(sulfonyl chloride), glycine, and KOH or triethylamine in the presence of Cu II ions. A self‐assembled (H 2 O) 30 cluster containing a puckered (H 2 O) 12 ring core was found in 2 , which presents a new mode of association of water molecules not predicted theoretically or previously observed experimentally. Furthermore, 2 forms a 2‐D supramolecular structure through hydrogen bonding and unique π–π stacking interactions. In 3 , there also exist discrete trimeric water clusters. The identity of the base determines the specific structural characteristics of 4 and 5 . When potassium hydroxide was used for the synthesis of 4 , it led to a 3‐D copper(II)–potassium(I) coordination polymer; when triethylamine was used, paddle‐wheel dinuclear units of copper(II) carboxylate were produced. Magnetic measurements show that there are weak antiferromagnetic interactions in 2 – 4 . In 5 the χ M T vs. T curve shows a minimum at 110 K and a climb from 110 K to 5 K, then a long‐range antiferromagnetic ordering occurs, as revealed by a decrease in χ M T with T . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)