Syntheses, Crystal Structures and Magnetic Properties of Carboxylato‐Bridged Polymeric Networks of MnII

Three new carboxylato‐bridged polymeric networks of MnII having molecular formula [Mn(ox)(dpyo)]n (1), {[Mn2(mal)2(bpee)(H2O)2]·0.5(bpee)·0.5(CH3OH)}n (2) and {[Mn3(btc)2(2,2′‐bipy)2(H2O)6]·4H2O}n (3) [dpyo, 4,4′‐bipyridine N,N′‐dioxide; bpee, trans‐1,2 bis(4‐pyridyl)ethylene; 2,2′‐bipy, 2,2′‐bipyridine; ox = oxalate dianion; mal = malonate dianion; btc = 1,3,5‐benzenetricarboxylate trianion] have been synthesized and characterized by single‐crystal X‐ray diffraction studies and low temperature magnetic measurements. Structure determination of complex 1 reveals a covalent bonded 2D network containing bischelating oxalate and bridging dpyo; complex 2 is a covalent bonded 3D polymeric architecture, formed by bridging malonate and bpee ligands, resulting in an open framework with channels filled by uncoordinated disordered bpee and methanol molecules. Whereas complex 3, comprising btc anions bound to three metal centers, is a 1D chain which further extends its dimensionality to 3D via ‐ and H‐bonding interactions. Low temperature magnetic measurements reveal the existence of weak antiferromagnetic interaction in all these complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)