By using the compartmental dinucleating pyrazolate ligand HL, dinickel(II) complexes [LNi2(micro-N3)(acetone)2]X2 (1: X = CIO4; 2: X = BPh4) and tetranickel(II) complex [{LNi2(micro-N3)(MeOH)2](CI04)4 (3) have been prepared and structurally characterized. Complexes 1 and 2 differ in the torsion along the bridging micro-1,3-azide moiety, while the azido ligands in 3 adopt an unusual micro-1,1,3 bridging mode to connect the two subunits. All three complexes show overall antiferromagnetic coupling and an S = 0 ground state, but the torsion along the azide moiety is a determining factor for the coupling strength. Compounds 1 and 2 serve as preorganized building blocks for the controlled synthesis of alternating 1D polymeric structures 4-6 by replacement of their labile acetone ligands by additional azido ligands. Due to the modular synthetic approach, 4-6 can be described as Heisenberg antiferromagnetic systems with inherent bond alternation (HABA), whereby the organic ligand framework ensures that the individual nickel/azido chains are well isolated in the crystal lattice. Like their precursors, 4-6 are mainly distinguished by torsion along the micro-1,3-azido bridges, both within and between the bimetallic constituents. Magnetic measurements confirm an overall 5 = 0 ground state for 4-6, and coupling parameters have been deduced from quantum Monte Carlo simulations. The two J values for the alternating 1D chains can be clearly assigned on the basis of the magnetostructural correlations established for the bimetallic building blocks. The alternation ratio gamma = J2J1(-1) places the three new systems in the HABA regime for a singlet-dimer ground state.