Seven one-dimensional (1D) coordination polymers {[Cd(HCOO)2(NioxH2)(bpe)].DMF}∞ (1), [Cd(HCOO)2(NioxH2)(bpe)]∞ (1a), [Zn(CH3COO)2(NioxH2)(bpe)(H2O)]∞ (2), [Cd(HCOO)2(NioxH2)(dps)]∞ (3), [Zn(CH3COO)2(NioxH2)(dps)]∞ (4), [Cd(CH3COO)2(NioxH2)(dps)]∞ (5), {[Zn(pyta)2(NioxH2)].DMF}∞ (6) (where NioxH2 = 1,2cyclohexanedionedioxime, bpe=4,4’-bipyridine ethane, dps=4,4’-dipyridylsulfide, Hpyta=(4pyridylthio)acetic acid, DMF=N,N’-dimethylformamide), were fabricated using ‘oxime/ carboxylate blend’ in the presence of bidentate pyridine ligands [1-2]. The use of zinc(II) or cadmium(II) sulfate resulted in one 1D ladder-type polymer {[Cd(SO4)(NioxH2)(bpy)](NioxH2).(H2O)3}∞ (7) (bpy = 4,4’-bipyridine) and three two-dimensional (2D) arrays with the compositions {[Zn(SO4)(NioxH2)(bpy)].0.5H2O.DMF}∞ (8), [Zn(SO4)(NioxH2)(bpe)]∞ (9), and [Cd(SO4)(NioxH2)(bpe)]∞ (10) [3-4]. The NioxH2 manifested itself as a useful co-ligand that is capable to fix the N2O2-square-distorted equatorial coordination environment of the d10 metals due to the chelate mode of its co-ordination through oximic nitrogen atoms and participation in the OH(oxime)…O(anion) hydrogen bonds, and in combination with the pyridine-type ligands it affords octahedral environments of the metal centers in the 1D and 2D coordination strands. This spacious ligand imposes the asymmetry around the metal center and together with the tetrahedral sulfate-anion provides the structural motifs in the form of chiral layers in 8-10. The bridging mode of sulfate-anion coordination to the metal center has a crucial impact on the dimensionality of the coordination compounds 7-10. The bulkiness of the NioxH2 molecule along with the conformational flexibility of its cyclohexyl ring provides an access to the loosely packed crystals capable to accumulate guest molecules such as water and DMF. The stability of 1 and 6 to the guest removal has been addressed experimentally, and the crystal-to-crystal transformation observed for 1 resulted in the guest free 1D polymer 1a which maintains its coordination network with the 10.3% unit cell volume contraction, while compound 6 remains unchangeable in the same conditions. These host−guest systems demon strate the luminescence response to the NioxH2 coordination and guest inclusion.