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)]·2CH3CN 1, {0.63[(H2O)(valen)Mn-μ1,3-N3−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.
H2valen 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.