A New Type of Supramolecular Assembly by Hydrogen Bond Templating: Identification of Rare Monodentate Acetate Coordination in [Fe 3 (µ 3 ‐O)(µ 2 ‐CH 3 COO) 6 (H 2 O) 2 (CH 3 COO)]·T·ClO 4 (T = 2,6‐Diaminopyridinium Cation, C 5 H 8 N 3 and 2‐Aminopyridinium Cation, C 5 H 7 N 2 )

The complexes [Fe 3 (µ 3 ‐O)(µ 2 ‐CH 3 COO) 6 (H 2 O) 2 (CH 3 COO)]· C 5 H 8 N 3 ·ClO 4 (C 5 H 8 N 3 = 2,6‐diaminopyridinium cation) ( 1 ) and [Fe 3 (µ 3 ‐O)(µ 2 ‐CH 3 COO) 6 (H 2 O) 2 (CH 3 COO)]·C 5 H 7 N 2 · ClO 4 (C 5 H 7 N 2 = 2‐aminopyridinium cation) ( 2 ) show novel self‐assembled supramolecular structures in their crystals as elucidated by X‐ray analysis. The structures contain [Fe 3 (µ 3 ‐O)(µ 2 ‐CH 3 COO) 6 (H 2 O) 2 (CH 3 COO)] units as the building blocks. A detailed examination of the structures revealed that monodentate acetate, which is stabilised by a hydrogen‐bond template T (2,6‐diaminopyridinium cation in 1 and the 2‐aminopyridinium cation in 2 ), plays a directing role in forming these new types of hydrogen‐bonded assemblies in 1 and 2 . Crystal data for 1 and 2 were determined by X‐ray structure analysis. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)