Two hexacoordinated dinuclear compounds [Mn(L1)(dca)] 2 (ClO 4 /PF 6 ) 2 ·CH 3 OH (1/2) and two heptacoordinated coordination polymers [Mn(L2)(dca)] n (ClO 4 /PF 6 ) n (3/4) [L1=N,N′-(bis-(pyridin-2-yl)benzylidene)-1,3-propanediamine; L2=N,N′-(bis-(pyridin-2-yl)benzylidene)diethylenetriamine; dca=dicyanamide] are synthesized and characterized. Structures of 1–3 have been solved by X-ray diffraction measurements. Each manganese(II) center in 1/2 is located in a distorted octahedral environment with an MnN 6 chromophore coordinated by the four N atoms of L1 and two nitrile N atoms of bibridged μ 1,5 dca. Interestingly, the coordination polymer 3 forms a 1D chain through single Mn–(NCNCN)–Mn units in which each manganese(II) center adopts a pentagonal bipyramidal geometry with an MnN 7 chromophore occupied with five N atoms of L2 and two nitrile N atoms of monobridged μ 1,5 dca. Magnetic susceptibility measurements of 1–3 in the 2–300K temperature range reveal weak antiferromagnetic interactions.