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The reaction of [HN(n-C4H9)3]3[WV(CN)8]·4H2O, 4,4′-bipyridine dioxide(4,4′-dpdo), and MnCl2·4H2O or CuCl2·2H2O gives two new three-dimensional octacyanometalate-based bimetallic assemblies, {[Mn2 (4,4′-dpdo)(H2O)4] [WIV(CN)8]}·6H2O (1) and {[Cu2(4,4′-dpdo)(H2O)][W(CN)8]}·CH3OH·H2O (2). Compound 1 crystallizes in the orthorhombic system, space group P21212 with cell constants a=10.397(2) -, b= 11.321(2) -, c=12.295(3) - and Z=2, whereas 2 crystallizes in the monoclinic system, space group P21/c with cell constants a=13.038(3) -, b=13.784(3) -, c=13.225(3) -, β=93.44(3)o and Z=4. In complex 1, each [WIV(CN)8]4- unit with a square antiprismatic geometry is connected to four Mn2 dimers through four bridging CN- ions forming wavelike alternating -W-Mn2-W-Mn2- layers, which are further linked through 4,4′-dpdo ligands coordinated to the Mn ions into a three-dimensional open framework. In complex 2, each [WIV(CN)8]4- ion still adopts a square antiprismatic geometry, whereas it bonds to seven copper ions through seven CN- ions leading to cage-like undulate layers further bridged by 4,4′-dpdo ligands into a three-dimensional network. Due to the bridging role of the long rigid 4,4′-dpdo ligand, there exist plenty of large cavities in the open frameworks of complexes 1 and 2 occupied by solvent clusters containing H2O or CH3OH molecules. To our knowledge, it is noted that 4,4′-dpdo displays a μ-4,4,4′,4′ m ode, which was first experimentally observed, although predicted before. Magnetic studies show that complex 1 displays an antiferromagnetic coupling between MnⅡ ions, while complex 2 ex-hibits a weak ferromagnetic interaction between CuⅡ ions.
The reaction of [HN (n-C4H9) 3] 3 [WV (CN) 8] · 4H2O, 4,4’- bipyridine dioxide (4,4’-dpdo), and MnCl2 · 4H2O or CuCl2 · 2H2O gives two new three-dimensional octacyanometalate-based bimetallic assemblies, {[Mn2 (4,4’-dpdo) (H2O) 4] [WIV (CN) 8]} 6H2O (1) and {[Cu2 (4,4’-dpdo) (H2O)] [W (CN) 8]} .CH3OH.H2O (2). Compound 1 crystallizes in the orthorhombic system, space group P21212 with cell constants a = 10.397 (2) -, b = 11.321 (2) c = 12.295 (3) - and Z = 2, whereas 2 crystallizes in the monoclinic system space group P21 / c with cell constants a = 13.038 (3) -, b = 13.784 (3) -, β = 93.44 (3) o and Z = 4. In complex 1, each [WIV (CN) 8] 4- unit with a square antiprismatic geometry is connected to four Mn2 dimers through four bridging CN- ions forming wavelike alternating - W-Mn2-W-Mn2-layers, which are further linked through 4,4’-dpdo ligands coordinated to the Mn ions into a three-dimensional open framework. In complex 2, each [WIV still adopts a square antiprismatic geometry, i t bonds to seven copper ions through seven CN- ions leading to cage-like undulate layers further bridged by 4,4’-dpdo ligands into a three-dimensional network. Due to the bridging role of the long rigid 4,4’-dpdo ligand, there exist plenty of large cavities in the open frameworks of complexes 1 and 2 occupied by solvent clusters containing H2O or CH3OH molecules. To our knowledge, it is noted that 4,4’-dpdo displays a μ-4,4,4 ’, 4’ m ode, which was first experimentally observed, although predicted before. Magnetic studies show that complex 1 displays an antiferromagnetic coupling between Mn II ions, while complex 2 ex-hibits a weak ferromagnetic interaction between Cu II ions.