In this study, neutral mercuryIJII) complexes of the composition ijHgIJL1)IJμ-Cl) 2 Hg 3 Cl 6 ] n (1), ijHgIJL1)IJμ-Br) 2 HgBr 2 ] (2), ijHgIJL3)Br 2 ] (2a), ijHgIJL1)I 2 ] (3), ijHgIJL2)Cl 2 ]ĴCH 3 OH (4) and ijHgIJL2)IJμ-Br)HgBr 3 ] 2 (5) (L1 = benzilbisIJ(pyridin-2-yl)methylidenehydrazone); L2 = benzilbisIJ(acetylpyridin-2-yl)methylidenehydrazone)) are described. Single-crystal X-ray crystallography showed that the molecular complexes can aggregate into larger entities depending upon the anion coordinated to the metal centre. Iodide gives discrete monomeric complexes, bromide generates a 1D coordination polymer formed through Hg-Br-Hg bridges and chloride gives rise to an inorganic-organic hybrid material. The significant differences in the reaction conditions indicate that the anions exert a substantial influence on the formation of the compoundssmaller anions show a larger potential for bridging metal ions and forming coordination polymers. A minute increase in the bulkiness of the ligand (two extra methyl substituents in L2) dramatically changes the coordination architectures, and leads to the formation of monomeric (chloride and iodide) and oligomeric (bromide) structures, rather than polymeric structures. The noncovalent C-H/π and π-hole interactions observed in the solid state architecture of some complexes have been rationalized by means of theoretical DFT calculations.CrystEngComm, 2015, 17, 3493-3502 | 3493This journal is