Three new metal-organic framework materials [Mg 3(LH) 2(EtOH) 2(H 2O)]·(EtOH) 4.5(H 2O) 0.25 (IMP-13Mg), [Co 3(LH) 2(EtOH) 2(H 2O)]·(EtOH) 3 (IMP-13Co), and [Ca 3(LH) 2(EtOH) 4]·(EtOH) 6 (IMP-14) have been prepared from the treatment of silanetetrabenzoic acid (L-H 4) with Mg II, Co II, and Ca II salts respectively. In all cases the silanetetrabenzoic acid has been triply deprotonated and the resultant carboxylate groups assemble with trinuclear metal-based nodes to give (3,6)-connected kgd-type two-dimensional layers. These layers are then extended into the third dimension by coordination of the metal nodes by carboxylic acid groups in adjacent layers. In the case of IMP-13Mg/Co, only alternate L-H connectors and metal nodes are involved in these interlayer interactions, leaving some acid groups free within the structure. However, in IMP-14 all L-H connectors and metal nodes participate in interlayer bonding.