Synthesis, Characterization, and Crystal Structure of Two Manganese Metallacrowns: 30‐Metallacrown‐10 and 18‐Metallacrown‐6 with Ligands Derived from 3‐Hydroxy‐2‐naphthalenecarbohydrazide

Two manganese metallacrowns [Mn 10 (pnhz) 10 (DMF) 4 (H 2 O) 6 ] · 10.5H 2 O · MeOH · DMF ( 1 ) and [Mn 6 (anhz) 6 (DMF) 2 (H 2 O) 4 ] · 6DMF ( 2 ), (H 3 pnhz = 3‐hydroxy‐ N ‐phenyl‐2‐naphthalenecarbohydrazide, H 3 anhz = N ‐acyl‐3‐hydroxy‐2‐naphthalenecarbohydrazide) have been prepared by the reactions of two pentadentate ligands, H 3 anhz and H 3 pnhz, with the corresponding manganese(II) salt, respectively, and characterized by elemental analysis, IR spectra, and X‐ray single‐crystal diffraction analysis. Complex 1 has an [Mn–N–N] 10 skeleton with two kinds of Mn III centers in an ··· AABAB ··· alignment, and the metallic centers exhibit a ··· ΔΛΔΛ ··· chiral configuration alignment. Adjacent molecules are linked by four intermolecular H bonds to form a 1D infinite chain structure. This is the first 1D supramolecular sample of a metallacrown formed by weak interactions. Complex 2 shows an [Mn–N–N] 6 skeleton with two kinds of Mn III centers in a ··· BAA ··· alignment. The successive manganese centers possess a ··· ΔΛΔΛ ··· chiral configuration alignment. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)