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Treatment of germanium dioxide with a 33% aqueous solution of 1,2-diaminopropane (DAP) under solvothermal conditions leads to the formation of colourless octahedral crystals of the novel germanate (1,2-DAPH 2 ) 2 Ge 9 (OH) 4 O 18  · 2 H 2 O. The compound crystallises in the orthorhombic space group Pbca, a = 14.4155(10), b = 12.9384(9), c = 14.5417(8) Å,V =2712.2 (3) Å 3 ; Z =4. The structure consists of an anionic [Ge 9 (OH) 4 O 18 ] 4−  framework with isolated [1,2-DAPH 2 ] 2+  cations and water molecules in the channels of the structure. The primary building units of the anionic framework are GeO 4  tetrahedra, GeO 5  trigonal bipyramids, and GeO 6  octahedra. The asymmetric unit consists of two GeO 5  units sharing a common edge to form a Ge 2 O 8  unit. This Ge 2 O 8  unit is corner-linked to two GeO 4  tetrahedra, and finally one GeO 4  tetrahedron is connected to a GeO 6  octahedron by cornersharing. The connectivity yields a chain-like Ge 5 O 19  fragment as a secondary building unit (SBU). The chain fragments are interconnected with each other forming the three-dimensional framework. Three types of channels with diameters ranging from 5.98 to 8.025 Å intersect the three-dimensional germanate network. Upon heating the compound decomposes in three steps starting at about 125˚C losing the water and the 1,2-diaminopropane molecules.

zeitschrift für naturforschung b

(1,2-DAPH 2 ) 2 Ge 9 (OH) 4 O 18  · 2H 2 O: A New Microporous Germanate Based on the Interconnection of Ge 9 O 18  Clusters Showing Reversible Water Emission and Uptake