Three types of heterometallic structural motifs based on [Mo(CN)8]3−/4− anion and MnII cation as building blocks

Abstract

The reaction between K3[Mo(CN)8] · H2O and MnCl2 · 4H2O in different reaction conditions have obtained three new bimetallic cyanide-bridged compounds, namely, {(tetrenH2)0.5[Mn(H2O)2][MoV(CN)8] · 2H2O}n (1) (where, tetren is tetraethylenepentamine), {[Mn2(H2O)4][MoIV(CN)8] · 3H2O}n (2), and {[Mn2(H2O)4][MoIV(CN)8] · 4H2O}n (3). Compound 1 crystallizes in the orthorhombic system with space group Cmc21 and unit cell constants a = 7.8234(15), b = 26.013(5), c = 10.021(2) A, β = 90°, and Z = 4. Compound 2 crystallizes in the monoclinic system with space group P21/n and unit cell constants a = 7.3329(11), b = 14.372(2), c = 18.070(3) A, β = 90.869(2)°, and Z = 4. Compound 3 crystallizes in the tetragonal system with space group I4/m and unit cell constants a = b = 11.9371(8), c = 13.2930(18) A, β = 90°, and Z = 4. X-ray single-crystal structures reveal that the Mo centers adopt a distorted square antiprism coordination environment for 1 and 3, while 2 closed to a bicapped trigonal prism. For these complexes, all the MnII centers in the extended structure adopt distorted octahedron geometry. For 1, each MoV coordinated via four cyanide groups to four MnII ions, and the other four cyanide groups are terminal, forming a two-dimensional framework. For 2, the MoIV center of structural unit coordinated via four cyanide groups to four Mn(1), and the other four cyanide groups coordinated to four Mn(2), forming a three-dimensional framework. For 3, each [MoIV(CN)8]4− building block is linked to MnII ions through its eight CN ligands, and each MnII center is connected to four Mo units forming a three-dimensional framework. In addition, magnetic studies of these complexes have also been presented.