<div><p>Two Zn<sup>II</sup> complexes, [Zn<sub>2</sub>(L)<sub>2</sub>(DMF)(H<sub>2</sub>O)<sub>2</sub>]·DMF (<b>1</b>) and [Zn(L)(DEF)]·DEF (<b>2</b>), were synthesized by solvothermal reactions using 4,4′-(2,3,5,6-tetramethylbenzene1,4-diyl)dibenzoic acid (H<sub>2</sub>L) and Zn(NO<sub>3</sub>)<sub>2</sub>·6H<sub>2</sub>O in different solvents of DMF, ethanol, and water for <b>1</b> and N,N-diethylformamide (DEF) for <b>2</b>. The L<sup>2−</sup> with different coordination modes connect [Zn<sub>2</sub>(COO)<sub>2</sub>] secondary building units (SBUs) to generate a wavy 2-D (4,4) network of <b>1</b> while in <b>2</b> there are paddlewheel [Zn<sub>2</sub>(COO)<sub>4</sub>] SBUs which are connected by L<sup>2−</sup> to form a planar 2-D (4,4) network. The 2-D layered structures show different stacking arrangements and are further linked by hydrogen bonding or C–H⋯π interactions to give 3-D architectures. The different structures and stacking arrangements of <b>1</b> and <b>2</b> result from different reaction solvents. Photoluminescence properties of the complexes were investigated.</p></div
