Chiral L-malate and achiral succinate ligands have been integrated into a three-dimensional homochiral framework by reacting transition-metal cations (Mn2+), L-(-)-malic acid (L-H(2)ma), succinic acid (H(2)suc), and 4,4'-bipyridine (4,4'-bipy). Chiral L-malate bonds to Mn2+ without using the -OH group, which is very unusual for malate. Such unusual bonding of chiral malate results from the cooperative effect of chiral malate and achiral succinate ligands during the self-assembly process, further assisted by the third complementary bipyridine ligand.