Upon addition of isopropanol (iPrOH) to an aqueous solution of the Li3BTC salt, a white precipitate of [Li3BTC • 5 H2O] (1 • 5H2O) coordination network was immediately formed, as evidenced by powder X-ray diffraction (PXRD) (Figure ). The high-quality rod-shaped single crystals of (1 • 5H2O) were prepared by slow diffusion of iPrOH vapors into the Li3BTC solution in mixture of water and THF. The single crystal X-ray diffraction experiment (SCXRD) allowed for detailed structural investigation of the 1 • 5H2O (P bca space group, details shown in Table ), which revealed that it forms 2D polymer layers perpendicular to the c axis. The tetrahedrallycoordinated lithium cations in 1 • 5H2O form two distinct SBU types: tetranuclear [Li4(O2CR)4 • 3H2O] cluster (Figure ) and polymeric [Li(O2CR) • 2H2O]n representing 1D chain structure (Figure ). The 2D coordination network layers in 1 • 5H2O are formed by connecting the SBUs using BTC linkers (Figure ). Finally, the AA-type stacked 3D structure in 1 • 5H2O (Figure ) is formed by supramolecular interactions between the 2D coordination networks. We note that the presented crystal structure of 1 • 5H2O appears similar to the results reported by Cheng el.al.. However, these similarities are difficult to evaluate since no crystal structure data of the corresponding material has been published. Therefore the crystal structure of 1 • 5 H2O has been presented here and deposited to the CCDC database accordingly. A [Na3BTC • 3H2O] (2 • 3H2O) coordination network was prepared by adding ethanol (EtOH) to an aqueous Na3BTC solution, which resulted in an immediate precipitation of 2 • 3H2O as white crystalline powder, as confirmed using PXRD (Figure ). High-quality single crystals of 2 • 3H2O could be prepared by slow diffusion of EtOH vapors to the aqueous Na3BTC solution, which allowed for the detailed structural investigations by SCXRD study (Table ). The solvate 2 • 3H2O crystallizes in the P21 space group and forms a 3D coordination network structure. The Na + cations in 2 • 3H2O are coordinated with 5 or 6 oxygen atoms forming distorted square pyramidal and octahedral motifs, respectively. The metal centers in 2 • 3H2O are linked by bridging carboxylate groups into complex SBUs: 2D layers extending in a direction perpendicular to the crystallographic b axis (Figure ). The 2D SBUs are interconnected by the organic linkers forming the layered 3D coordination network structure (Figure ). An aqueous solution of the K3BTC salt was used to prepare a hydrated [K3BTC • 3 H2O] (3 • 3H2O) coordination network, which was precipitated upon addition of iPrOH, as shown by PXRD study (Figure ). Single crystals of 3 • 3H2O were prepared by exposition of the aqueous K3BTC solution to the iPrOH vapors, allowing for the detailed SXCRD study (Table ), which revealed that 3 • 3H2O crystallizes in the P21/c space group and forms a 3D coordination polymer. The K + cations in the 3 • 3H2O structure were coordinated by 6-8 oxygen atoms originating from carboxylate groups and water molecules. Interestingly, the SBU, defined as the collection of metal centers bridged by the carboxylate groups, extends indefinitely in all three directions in the crystal structure of 3 • 3H2O (Figure ). Overall, we demonstrated a range of new crystalline alkali-BTC coordination networks prepared by the simple aqueous synthetic route. The observed trends in the local coordination environment of metal cations were in agreement with the literature reports on alkali metal-based carboxylates. Namely, lithium cation were always coordinated by four oxygen atoms in a quasi-tetrahedral geometry, while the heavier cations exhibited increasingly complex coordination geometries adopting up to 6 and 8 coordinated oxygen atoms for sodium and potassium, respectively. Moreover, the complexity of observed SBUs was also dependent on the cation type ranging from 0D and 1D SBUs for lithium-based networks to 3D SBUs for potassium.