Structural Analysis, Spectroscopic, and Magnetic Properties of the 1D Triple-Bridged Compounds [M(dca)2(bpa)] (M = Mn, Fe, Co, Zn; dca = dicyanamide; bpa = 1,2-bis(4-pyridyl)ethane) and the 3D [Ni(dca)(bpa)2]dca·6H2O

• Published in: Inorganic chemistry 2010-11, Vol.49 (22), p.10445-10454
• Main Authors: de la Pinta, Noelia, Martín, Susana, Urtiaga, M. Karmele, Barandika, M. Gotzone, Arriortua, M. Isabel, Lezama, Luis, Madariaga, Gotzon, Cortés, Roberto
• Format: Article
• Language: English
• Subjects: Bridged-Ring Compounds - chemical synthesis; Bridged-Ring Compounds - chemistry; Cobalt - chemistry; Crystallography, X-Ray; Cyanamide - chemistry; Iron - chemistry; Magnetics; Manganese - chemistry; Metals, Heavy - chemistry; Models, Molecular; Molecular Structure; Pyridines - chemistry; Zinc - chemistry
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic1014626

The family of compounds [Mn(dca)2(bpa)] (1), [Fe(dca)2(bpa)] (2), [Co(dca)2(bpa)] (3), [Zn(dca)2(bpa)] (4), and [Ni(dca)(bpa)2]dca·6H2O (5), with dca = dicyanamide and bpa = 1,2-bis(4-pyridyl)ethane, has been synthesized. These compounds have been characterized by single crystal (1, 2, 4, and 5) and powder X-ray diffraction (3), by Fourier transform infrared (FTIR), UV−vis, and electron paramagnetic resonance (EPR) spectroscopies, and by magnetic measurements. Compound 1 crystallizes in the monoclinic C2/c space group, Z = 4, with a = 16.757(6), b = 9.692(3), and c = 13.073(4) Å, and β = 123.02(2)°; Compound 2 crystallizes in the monoclinic C2/c space group, Z = 4, with a = 16.588(5), b = 9.661(3), c = 12.970(5) Å, and β = 123.16(3)°; Compound 4 crystallizes in the monoclinic C2/c space group, Z = 4, with a = 16.519(2), b = 9.643(2), c = 12.943(2) Å, and β = 123.15(1)°; Compound 5 crystallizes in the monoclinic C2/c space group, Z = 4, with a = 18.504(4), b = 19.802(3), and c = 8.6570(18) Å, and β = 99.74(2)°. The compounds 1−4 are isostructural and show a one dimensional (1D) disposition, with the metal(II) ions bridged by double μ1,5 dca ligands and unusually by a third bridge consisting of the bpa ligand, which adopts a very low torsion angle to accommodate in the structure. This kind of structure is unusual, even considering the voluminous bpa bridge. The compound 5 shows a 3D structure with layers of Ni-bpa joined by single dca bridges. Magnetic susceptibility measurements show antiferromagnetic couplings, increasing for 1−3. Compound 5 shows very slight antiferromagnetic interactions.