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

One novel N-[(3-carboxyphenyl)sulfonyl]glycine (H3L1) ligand (1) was prepared in high yield, and its structure was determined by single-crystal X-ray diffraction. Reaction of H3L1 with Mn(ClO4)2·6H2O at different pH values gave two new dinuclear complexes: [Mn2(HL1)2(phen)4]·16H2O (2) and [Mn2L1(phen)4(H2O)]ClO4·3H2O (3) (phen = 1,10-phenanthroline). Additionally, two copper(II) complexes, [K2Cu(L2)2(H2O)2]n (4) and [CuL2(H2O)]2·2H2O (5), involving another novel ligand, N,N′-(1,3-phenylenedisulfonyl)bis(glycine) (H2L2), were prepared by a one-pot reaction of 1,3-phenylenebis(sulfonyl chloride), glycine, and KOH or triethylamine in the presence of CuII ions. A self-assembled (H2O)30 cluster containing a puckered (H2O)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 χMT 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 χMT with T. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)