Structure and Magnetism of 3D Anionic Metal Dicyanamide (MePh<sub>3</sub>P)[M(dca)<sub>3</sub>] (M = Fe, Co, Ni) and (EtPh<sub>3</sub>P)[M(dca)<sub>3</sub>] (M = Mn, Co, Ni) Networks

The structures of (MePh<sub>3</sub>P)[M(dca)<sub>3</sub>] (M = Fe, Co, Ni and dca = dicyanamide, N(CN)<sub>2</sub><sup>-</sup>) are isomorphous and contain anionic [M(dca)<sub>3</sub>]<sup>-</sup> networks in which octahedral metal ions are bridged by bidentate μ<sub>1,5</sub> dca anions, to generate three-dimensional (3D) five-connected networks. The structures of (EtPh<sub>3</sub>P)[M(dca)<sub>3</sub>] (M = Mn, Co, Ni) are also isomorphous and contain similar anionic networks to the MePh<sub>3</sub>P<sup>+</sup> structures. In both sets of structures, the cations appear to perform a templating function and lie in pairs within cavities in the anionic network. These cation pairs show pseudo-6-fold phenyl embraces. No long-range magnetic ordering intrinsic to these materials was observed, although traces of the ferromagnets α-[Co(dca)<sub>2</sub>] and α-[Ni(dca)<sub>2</sub>] were observable in very small applied fields, at 9 and 21 K, respectively.