At the same condition, utilizing the different of base, the authors constructed two wholly different compounds, 1 and 2. Compounds 1 and 2 are one-dimensional (1D) chainlike, while the coordination mode of dicyandiamide is different in both complexes. In 1, the dicyandiamide is μ 1,5-dca bridged coordination mode; in 2, that is μ 1,3-dca bridged coordination mode. Two new heterobinuclear nickel and sodium polymers [NiN a(L)(dca)] n (1) and [NiNa(L)(dca)] 2n ·(CH3COOCH3) n ·(H2O) n , (2) [where H2L = N,N′-bis(3-ethoxy- salicylidene)ethylenediamine, dca = N(CN)2 –], were synthesized and characterized by elemental analysis and X-ray crystal diffraction. The heterobinuclear complex 1, C22H22N5NaNiO4, crystallizes in the monoclinic system space group P21 /c, with a = 8.0955 (7) Å, b = 22.1988 (18) Å, c = 12.9314 (11) Å; β = 103.4700(10)°; Z = 4; S = 1.01; V = 2260.0(3) Å3; D Calcd = 1.476 gcm–3; F(000) = 1040; μ = 0.92 mm–1; R 1 = 0.041; wR 2 = 0.104. The complex 2, C23.50H27N5NaNiO5.50, the crystals belong to the monoclinic system, space group C2/c, with a = 31.553 (8) Å, b = 12.836 (3) Å, c = 13.264 (3) Å; β = 111.234 (4)°; Z = 8; S = 0.95; V = 5007.6 (19)Å3; D Calcd = 1.457 gcm–3; F(000) = 2288; μ = 0.84 mm–1; R 1 = 0.072; wR 2 = 0.211. Complexes 1 and 2 are both axisymmetric heterobinuclear nickel complexes. The geometry around nickel atoms can be described as a slightly distorted plane geometry, and sodium atoms that as a slightly distorted octahedral geometry. Complexes 1 and 2 are both one-dimensional (1D) chainlike supramolecular structure bridged by dicyandiamide to form the polymer. The coordination mode of dicyandiamide is different in both complexes. In 1, the dicyandiamide is μ1,5-dca bridged coordination mode; in 2, that is μ1,3-dca bridged coordination mode by dicyandiamide. Supplemental materials are available for this article. Go to the publisher's online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.