Abstract: | One binuclear complex Co(bpm*)2(dca)]2(ClO4)2 ( 1 ) and two 1D chain CoII complexes, {Co(bpm)2(dca)](ClO4)}n ( 2 ) and Co(dmf)2(dca)2]n ( 3 ), (bpm*: bis(3, 5‐dimethyl)pyrazolyl]methane; bpm: bis(pyrazolyl)methane; dca: dicyanamide; dmf: N, N‐dimethyl formamide) have been prepared and structurally characterized. The cobalt atoms are hexa‐coordinated forming a slightly distorted octahedral coordination. Compound 1 crystallizes in the monoclinic system, space group P21/c, a = 9.849(3)Å, b = 21.944(7)Å, c = 13.814(5)Å, β = 94.824(6), Z = 4, R1 = 0.0672, wR2 = 0.1395. 1 is a binuclear complex linked by two dca ligands, and each CoII ion is coordinated by two terminal bpm* ligands. Compound 2 crystallizes in the orthorhombic system, space group Cmcm, a = 10.377(4)Å, b = 13.594(5)Å, c = 15.999(6)Å, Z = 4, R1 = 0.0609, wR2 = 0.1328. The structure of 2 can be described as a one‐dimensional zigzag chain of CoII ions bridged by one dca ligand. Each CoII ion in the chain is coordinated by two bpm ligands. Compound 3 crystallizes in the monoclinic system, space group C2, a = 13.559(15)Å, b = 7.393(8)Å, c = 8.110(9)Å, β = 112.228(15), Z = 2, R1 = 0.0260, wR2 = 0.0760. 3 has a one‐dimensional linear chain of CoII ions bridged by two dca ligands, in which each CoII ion is coordinated with two dmf molecules. |