Two novel polymers exhibiting metal–organic frameworks (MOFs) have been synthesized by the combination of a metal ion with a benzene-1,3,5-tricarboxylate ligand (BTC) and 1,10-phenanthroline (phen) under hydrothermal conditions. The first compound, poly[[(μ4-benzene-1,3,5-tricarboxylato-κ4
O:O′:O′′:O′′′)(μ-hydroxido-κ2
O:O)bis(1,10-phenanthroline-κ2
N,N′)dizinc(II)] 0.32-hydrate], {[Zn2(C9H3O6)(OH)(C12H8N2)2]·0.32H2O}
n
, denoted Zn–MOF, forms a two-dimensional network in which a binuclear Zn2 cluster serves as a 3-connecting node; the BTC trianion also acts as a 3-connecting centre. The overall topology is that of a 63 net. The phen ligands serve as appendages to the network and interdigitate with phen ligands belonging to adjacent parallel sheets. The second compound, poly[[(μ6-benzene-1,3,5-tricarboxylato-κ7
O
1,O
1′:O
1:O
3:O
3′:O
5:O
5′)(μ3-hydroxido-κ2
O:O:O)(1,10-phenanthroline-κ2
N,N′)dimanganese(II)] 1.26-hydrate], {[Mn2(C9H3O6)(OH)(C12H8N2)]·1.26H2O}
n
, denoted Mn–MOF, exists as a three-dimensional network in which an Mn4 cluster serves as a 6-connecting unit, while the BTC trianion again plays the role of a 3-connecting centre. The overall topology is that of the rutile net. Phen ligands act as appendages to the network and form the `S-shaped' packing mode.