Syntheses and Characterization of Diammine–Nickel/Cobalt(II)–Bisdicyanamide M(NH3)2[N(CN)2]2 with M = Ni and Co

Crystals of M­(NH3)2[N­(CN)2]2 with M = Ni and Co were obtained from the reaction of stoichiometric amounts of Na­[N­(CN)2] with NiCl2·6H2O or CoCl2·6H2O in aqueous, ammoniacal solutions. X-ray single-crystal structure analyses show that M­(NH3)2[N­(CN)2]2 with M = Ni and Co crystallize isotypically to each other and adopt the monoclinic space group P21/c (no. 14). The lattice parameters of Ni­(NH3)2[N­(CN)2]2 are a = 5.8498(9) Å, b = 10.6739(12) Å, and c = 6.8089(17) Å, β = 98.037(3)° and Z = 2, while those of Co­(NH3)2[N­(CN)2]2 are a = 5.8303(11) Å, b = 10.746(2) Å, c = 6.7773(13) Å, and β = 96.422(3)°. In addition, the crystal structure of the nickel compound was refined from neutron powder diffraction, augmented by DFT calculations as regards atomic displacement parameters. The IR spectra of the title compounds exhibit modes typical for the dicyanamide anion and ammonia. The UV/vis spectrum of Ni­(NH3)2[N­(CN)2]2 shows that the dicyanamide moiety is a medium-field ligand. Additional superconducting quantum interference device (SQUID) magnetic susceptibility measurements of Ni­(NH3)2[N­(CN)2]2 and Co­(NH3)2[N­(CN)2]2 confirm not only significant high-spin moments of χm T = 1.24 cm3·K·mol–1 (μeff = 3.15 μB) and 2.89 cm3·K·mol–1 (μeff = 4.81 μB), respectively, at 290 K and 0.1 T but also an absence of magnetic ordering.