Zn/Mn–MOFs with `S-shaped' packing modes

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[[(μ 4 -benzene-1,3,5-tricarboxylato-κ 4 O : O ′: O ′′: O ′′′)(μ-hydroxido-κ 2 O : O )bis(1,10-phenanthroline-κ 2 N , N ′)dizinc(II)] 0.32-hydrate], {[Zn 2 (C 9 H 3 O 6 )(OH)(C 12 H 8 N 2 ) 2 ]·0.32H 2 O} n , denoted Zn–MOF, forms a two-dimensional network in which a binuclear Zn 2 cluster serves as a 3-connecting node; the BTC trianion also acts as a 3-connecting centre. The overall topology is that of a 6 3 net. The phen ligands serve as appendages to the network and interdigitate with phen ligands belonging to adjacent parallel sheets. The second compound, poly[[(μ 6 -benzene-1,3,5-tricarboxylato-κ 7 O 1 , O 1′ : O 1 : O 3 : O 3′ : O 5 : O 5′ )(μ 3 -hydroxido-κ 2 O : O : O )(1,10-phenanthroline-κ 2 N , N ′)dimanganese(II)] 1.26-hydrate], {[Mn 2 (C 9 H 3 O 6 )(OH)(C 12 H 8 N 2 )]·1.26H 2 O} n , denoted Mn–MOF, exists as a three-dimensional network in which an Mn 4 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.