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The syntheses, structures and magnetic properties of the compounds of formulae [Mn((R)-salmen)(CH3OH)(CH3CN)][MnCr(ox)3](CH3OH)0.5(CH3CN)1.25 ((R)-1), [Mn((S)-salmen)(CH3OH)(CH3CN)][MnCr(ox)3](CH3OH)0.5(CH3CN)1.25 ((S)-1), [Mn((R)-salmen)(CH3OH)2][MnCr(ox)3](CH2Cl2)0.375(CH3OH)0.125(H2O)0.375 ((R)-2) and [Mn((S)-salmen)(CH3OH)2][MnCr(ox)3](CH2Cl2)0.375(CH3OH)0.375(H2O)0.125 ((S)-2) (ox = oxalate, salmen2− = N,N′-(1-methylethylene)bis(salicylideneiminate)), [Mn(salpn)(CH3OH)1.5(CH3CN)0.5][MnCr(ox)3](CH3OH)0.82(H2O)0.93 (3) (salpn2− = N,N′-(propane)bis(salicylideneiminate)) and [Mn(saltmen)(CH3OH)(CH3CN)][MnCr(ox)3](CH3OH) (4) (saltmen2− = N,N′-(1,1,2,2-tetramethylethylene)bis(salicylideneiminate)) are reported. These compounds are prepared by the insertion of MnIII–Schiff base complexes into bimetallic oxalate networks. Different types of bimetallic oxalate networks are obtained for each templating cation. Thus, [Mn((R)-salmen)]+ and [Mn((S)-salmen)]+ chiral templating cations give rise to a 2D chiral bimetallic oxalate layer in acetonitrile in (R)-1 and (S)-1 compounds, whereas a new type of achiral 3D oxalate network is obtained with the same templating cation in dichloromethane in (S)-2 and (R)-2. On the other hand, [Mn(salpn)]+ and [Mn(saltmen)]+ give rise respectively to a 3D chiral network and a 2D achiral network in compounds 3 and 4. The magnetic properties of the four compounds indicate that they undergo a long-range ferromagnetic ordering at ca. 5 K.
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