Supramolecular dimers and chains resulting from second coordination sphere interactions

Three new complexes of manganese(III) have been synthesized and crystallographically characterized: [Mn(valen)-(H2O)(NCS)] ·2CH3CN1,{0.63[(H2O)(valen)Mn-μ1,3-N 3 - Mn(valen)(H2O)]}{0.37{[Mn(valen)(H2O) 2][Mn(valen)(H2O)(N3)]}(ClO4)-(CH3 OH) 2 (0.63 and 0.37 are the occupation factors for the disordered azido group), and [(H2O)(valen)Mn - NCAgCN]·H2O 3. H 2valen is a bicompartimental Schiff base proligand, resulting from the 2:1 condensation of 3-methoxysalicyladehyde with ethylenediamine. The packing of these complexes in the crystals is governed by second coordination sphere interactions. The complex species are self-complementary: one aqua ligand from one complex can be hosted into the free compartment (O2O' 2) of a similar complex. Supramolecular dimers result in the case of complex 1. The packing of the azido-bridged dimers in 2 affords supramolecular chains. In the case of compound 3, the hydrogen-bonded dimers are further connected through Ag⋯Ag interactions, resulting in supramolecular chains. The crystallization water molecules in crystal 3 are grouped in almost planar hexamers. The magnetic properties of complexes 1 and 2 are discussed. © 2007 American Chemical Society.