Two copper metallo-ligands [CuL1(H2O)] and [CuL2-(H2O)] [H2L1 = N,N′-ethylenebis(3-methoxysalicylaldimine) and H2L2 = N,N′-ethylenebis(3-ethoxysalicylaldimine)] have been utilized for the preparation of heterobimetallic eight CuIISnIV complexes [CuL1]2·[SnMe2Cl4]2-·(H2ED)2+ (1), [CuL1]2·[SnEt2Cl4]2-·(H2ED)2+·0.5H2O (2), [CuL1]2·[Sn(n-Bu)2Cl4]2-·(H2ED)2+ (3), [CuL1]2·[SnPh2Cl4]2-·(H2ED)2+ (4), [CuL1]2·[SnPh2Cl4]2-·(H2ED)2+·2MeOH (5), [CuL2]2·[SnMe2Cl2(H2O)2]·0.2H2O (6), [CuL2]·[Sn(n-Bu)2Cl2(H2O)] (7), [CuL2]2·[SnPh2Cl4]2-·(H2ED)2+ (8), and two CuIISnII systems [CuL1SnCl]+·[SnCl3]- (9) and [CuL2SnCl]+·[SnCl3]- (10) (ED = 1,2-ethylenediamine). Single crystal X-ray structure analyses indicate that 1-5 and 8 are three-component [1×2+1×1+1×1] salt cocrystals of two neutral mononuclear [CuL1]/[CuL2] moieties, one organometallic dianion [SnR2Cl4]2- (R = Me, Et, n-Bu, and Ph), and one doubly protonated 1,2-ethylenediammonium dication H2ED2+, while compounds 6 and 7 are two-component [1×2+1×1]/[1×1+1×1] cocrystals of one/two neutral mononuclear [CuL2] and one neutral organotin(IV) moieties. Compounds 9 and 10 are two-component salts which are comprised of heterometallic, diphenoxido-bridged, dinuclear CuIISnII cation [CuLSnCl]+ and SnII anionic residue [SnCl3]-. Interestingly, the formation of the salt cocrystals or cocrystals 1-8 and salts 9 and 10 can be well rationalized in terms of several noncovalent weak interactions (O-H···O/N-H···O/N-H···Cl/Cu···Cl/Sn···Cl/Sn···Cu/π···π) which result in the generation of a tetrameric associate in 7, one-dimensional topology in 3-5 and 8-10 and two-dimensional supramolecular associate in 1 and 2. The first metallo-ligand [CuL1(H2O)] produces similar three-component CuII···SnIV···diprotonated diamine salt cocrystals (1-5), attesting to the selectivity toward the formation of this type of compound, while the latter one [CuL2-ing;(H2O)] displays a diverse structure forming capability by producing a CuII···SnIV···diprotonated diamine salt cocrystal (8) and two CuII···SnIV cocrystals (6 and 7). Interestingly, no such selectivity is observed for their heterometallic CuIISnII derivatives (9 and 10) which are similar two-component salts and completely different from 1-8. The current study illustrates an excellent example of structural diversity in heterometallic CuIISnII/IV complexes depending on the ligand substitution and metal oxidation state. Moreover, a heterometallic system, such as 1-5 and 8, containing ammonium-stannate adduct (X-NH3·SnX6, X = any) is not known according to the search made on the Cambridge Structural Database (CSD). © 2016 American Chemical Society.