Two new compounds of general formula [M(N₃)₂(dmbpy)] in which dmbpy = 5,5′-dimethyl-2,2′-bipyridine, and M = Mn(II) or Co(II), have been solvothermally synthesized and characterized structurally and magnetically. The structures consist of zig-zag polymeric chains with alternating bis-µ(azide-N1)₂M and bis-µ(azide-N1,N3)₂M units in which the cis-octahedrally based coordination geometry is completed by the N,N’-chelating ligand dmbpy. The molecular structures are basically the same for each metal. The Mn(II) compound has a slightly different packing mode compared to the Co(II) compound, resulting from their different space groups. Interestingly, relatively weak interchain interactions are present in both compounds and this originates from π–π stacking between the dmbpy rings. The magnetic properties of both compounds have been investigated down to 2 K. The measurements indicate that the manganese compound shows spin-canted antiferromagnetic ordering with a Néel temperature of T_N = 3.4 K and further, a field-induced magnetic transition of metamagnetism at temperatures below the T_N. This finding affords the first example of an 1D Mn(II) compound with alternating double end-on (EO) and double end-to-end (EE) azido-bridged ligands, showing the coexistence of spin canting and metamagnetism. The cobalt compound shows a weak ferromagnetism resulting from a spin-canted antiferromagnetism and long-range magnetic ordering with a critical temperature, T_C = 16.2 K.

Dicyanamides of d-metals provide a wide range of magnetic properties tuned by external cations, encapsulated ions, and coordination modes of anions. Analysis of molecular, one-periodic (1D chain), two-periodic (2D layered), and three-periodic (3D framework) networks formed by transition metals in their dicyanamides was carried out. All dicyanamides were treated as systems of nodes (metal centers and polytopic ligands) and spacers (bridge dicyanamide anions and co-ligands). The most typical coordination numbers, the role of the dicyanamide, and the effect of terminal and chelate co-ligands on the dimensionality and type of overall architecture were described. A knowledge-based system to predict possible architectures of novel dicyanamides was described and tested on samples of five complexes. The synthesis and spectroscopic and structural properties of the synthesized compounds were described. It was demonstrated that the novel compounds realize square lattice (sql), honeycomb (hcb) or simple chain (2C1) motifs, which were estimated to be the 1st and the 2nd of the most abundant topologies for 2D networks and the most expected 1D motif, respectively.

The search for new molecular materials with interesting magnetic properties using the pseudohalide azide ion and quinolin-8-amine (aqin, C₉H₈N₂) as a chelating ligand, led to the synthesis and structure determination of the title complex, [Fe(N₃)₂(C₉H₈N₂)₂]. The complex shows an octahedral geometry, with the Fe^II atom surrounded by six N atoms; the two N₃ ⁻ anions coordinate in a cis configuration, while the remaining N atoms originate from the two quinolin-8-amine ligands with the quinoline N atoms lying on opposite sides of the Fe atom. The crystal packing is dominated by layers of hydrophilic and aromatic regions parallel to the ac plane, stabilized by a two-dimensional hydrogen-bonded network and π–π stacking.