The systematic exploration of the phase diagram of the GeO2-1,6-diaminohexane-water-pyridine-HF system has allowed the identification of specific roles of the HF, H2O contents, and HF/H2O ratio in the formation of Ge7X19 (Ge-7), Ge9X25-26 (Ge-9), and Ge10X28 (Ge-10) clusters (X = 0, OH, F). This work has led to the discovery of two novel structures with extra-large 18-membered rings accommodating 1,6-diaminohexane (DAH): SU-63, 11.5H(2)DAHI-[Ge7O14X3].2H(2)O, a layered germanate constructed from Ge-7 clusters with the Kagome topology, and SU-64, I 11H(2)DAHI[Ge9O18X4][Ge7O14X3](6).16H(2)O, a germanate built of two-dimensional slabs containing both Ge-7 and Ge-9 clusters (X = OH or F). We also put SU-64 in context with previously reported cluster germanate compounds with related topologies by means of a simple crystal deconstruction study.