Extended Networks of Co2+ and Mn2+ Bridged by NCS–/N3– Anions and Flexible Long Spacers: Syntheses, Structures, and Magnetic Properties

Four new metal‐organic polymers with SCN–/N3– anion bridges and flexible long spacers L {L = bim [1,2‐bis(imidazol‐1‐yl)ethane] and bte [1,2‐bis(1,2,4‐triazol‐1‐yl)ethane]}, [Co(SCN)2(bim)] (1‐Co), [Co(SCN)2(bte)] (2‐Co), [Mn(N3)2(bte)] (3‐Mn), and [Mn(N3)2(bim)] (4‐Mn), were synthesized and characterized by single‐crystal X‐ray diffraction studies and their magnetic properties were investigated. Complex 1‐Co is a triple‐bridging chain complex with double end‐to‐end SCN– anions and single gauche‐bim spacers as bridges. Complexes 2‐Co and 3‐Mn both contain 1D chains bridged by double end‐to‐end SCN– or N3– anions and these chains are further extended to 2D (4,4) layers by the anti‐bte spacers. Complex 4‐Mn has a topological 3D diamond structure constructed through 1D double end‐on azide‐bridged MnII chains and extended through the anti‐bim spacers. Magnetic measurements reveal that 1‐Co and 3‐Mn remain paramagnetic; the dominant magnetic coupling between CoII is weak ferromagnetic and that between MnII is strong antiferromagnetic. As for 2‐Co and 4‐Mn, they show metamagnetic behavior below TN = 2.9 and 3.0 K, respectively. Our results show that a combination of the short anion bridges (SCN–/N3–) and flexible bidentate long spacers can be used to construct coordination polymers with novel topologies and interesting magnetic properties. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)