The reactions of Zn(OAc)(2)center dot 2H(2)O with various positional isomers of lutidine were explored with a view to understand the factors responsible for the nuclearity/aggregation and acetate coordination modes of the products. The reactions of Zn(OAc)(2)center dot 2H(2)O with 3,5-lutidine, 2,3-lutidine, 2,4-lutidine, and 3,4-lutidine in a 1:1 ratio in methanol at ambient temperature afforded three discrete trinuclear complexes [Zn-3(OAc)(2)(mu(2)-eta(2):eta(1)-OAc)(2)(mu(2)-eta(1):eta(1)-OAc)(2)(H2 O)(2)(3,5-lutidine)(2)] (1), [Zn-3(mu(2)-eta(1):eta(1)-OAc)(4)(mu(2)-eta(2):eta(0)-OAc)(2)L-2] [L = 2,3-lutidine (2) and 2,4-lutidine (3)], and a one-dimensional coordination polymer [Zn(OAc)(mu(2)-eta(1):eta(1)-OAc)(3,4-lutidine)] (4) in 93, 79, 81, and 94% yields, respectively. Complexes 1-4 were characterized by microanalytical, IR, solution (H-1 and C-13), and solid-state cross-polarization magic angle spinning C-13 NMR spectroscopic techniques and single-crystal X-ray diffraction data. Complex 1 is unique in that it contains three types of acetate coordination modes, namely, monodentate, bridging bidentate, and asymmetric chelating bridging, Variable-temperature H-1 NMR data indicated that complex 1 partially dissociates in solution, and the remaining undissociated 1 undergoes a rapid "carboxylate shift" even at 218 K. The plausible mechanism of formation of complexes 1-4 was explained with the aid of a point zero charge (pzc) model, according to which the nuclearity/aggregation observed in complexes 1-4 depends upon the number and nature of equilibrating species formed upon dissolution of the reactants in methanol, and these in turn depend upon the subtle basic/steric properties of lutidines. Further, noncovalent interactions play a crucial role in determining the nuclearity/aggregation and acetate coordination modes of the products.