From aqueous solutions containing Λ-[Co(en) 3 ]I 3 (1, 2), Δ-[Co-(en) 3 ]I 3 (5), or racemic [Co(en) 3 ]I 3 (3, 4) AgI and PbI 2 respectively were precipitated by addition of Ag 2 EDC, [Ag(en)][Ag(BDC)], PbADC or (NH 4 )[Ag 5 (BTC) 2 (NH 3 )-(H 2 O) 2 ] and filtered off (en = ethylenediamine, H 2 EDC = fumaric acid, H 2 BDC = terephthalic acid, H 2 ADC = acetylenedicarboxylic acid, H 3 BTC = trimesic acid). After slow evaporation of the remaining solutions single crystals of ∞ 1and ∞ 2 {Δ-[Co(en) 3 ]EDC(NO 3 )}•2H 2 O (C2, Z = 4, 5) were obtained. In all compounds the [Co(en) 3 ] 3+ cores are connected in a T-shaped mode via N−H•••O hydrogen bonds to the carboxylates to form complex networks. Water molecules are bound via O−H•••O hydrogen bonds to the networks, further increasing their complexity. It is noteworthy that the chirality of the starting material (Λ-or Δ-[Co(en) 3 ]I 3 ) is maintained during the reaction thus leading to non-centrosymmetric polymers, whereas with racemic [Co(en) 3 ]I 3 centrosymmetric polymers are obtained.