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Correlative studies of three oxalato-bridged polymers, obtained under hydrothermal conditions for the two isostructural compounds {Rb(HC2O4)(H2C2O4)(H2O)2}∞1, 1, {H3O(HC2O4)(H2C2O4).2H2O}∞1, 2, and by conventional synthetic method for {Rb(HC2O4)}∞3, 3, allowed the identification of H-bond patterns and structural dimensionality. Ferroïc domain structures are confirmed by electric measurements performed on 3. Although 2 resembles one oxalic acid sesquihydrate, its structure determination doesn’t display any kind of disorder and leads to recognition of a supramolecular network identical to hybrid s-block series, where moreover, unusual H3O+ and NH4+ similarity is brought out. Thermal behaviors show that 1D frameworks with extended H-bonds, whether with or without a metal center, have the same stability. Inversely, despite the dimensionalities, the same metallic intermediate and final compounds are obtained for the two Rb+ ferroïc materials.

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The structure of the title compound, [La(C5H6O4)(C5H7O4)‐(H2O)]·H2O, consists of dense layers formed by chains of one‐edge‐sharing LaO9(H2O) polyhedra, linked together by the glutarate ligand. The three‐dimensional polymeric structure, built up through connection of these layers by the hydrogen glutarate ligand, exhibits cavities accommodating a guest water mol­ecule. The lanthanum ion is tenfold coordinated by four glutarates, acting as bridging–chelating carboxyl­ate groups, by three hydrogen glutarates, three times monodentate, and by one water mol­ecule. Its coordination polyhedron is highly distorted and intermediate between a bicapped dodecahedron and a tetracapped trigonal prism. Hydro­gen bonding links the two water mol­ecules and the framework built up from this polynuclear coordination polymer. A very short hydrogen bond, D⋯A = 2.484 (3) Å, links the proton­ated with the deprotonated acid groups in the hydrogen glutarate.

The title compound, [La2(C3H2O4)3(H2O)4]·H2O, forms a layer‐type polymeric structure. The layers, which contain infinite puckered four‐membered La—O—La—O rings in a pseudo‐ternary symmetry, are formed by the lanthanum and one independent malonate group. They are interconnected by the second independent malonate group, giving a three‐dimensional framework in which wide channels accommodate one disordered water mol­ecule of crystallization. The La atom lies on a twofold axis and is ten‐coordinated by eight O atoms from carboxyl­ate groups and two water mol­ecules. One malonate group is monodentate and triply bridging chelating, whilst the other is doubly monodentate. The extensive network of hydrogen bonds and bridge bonds observed in this structure enhances the structural stability. Despite some identical subfeatures, this structure is quite different from that observed in [La2(C3H2O4)3(H2O)3]·2H2O.