Poly[diaquadi‐μ6‐oxalato‐μ5‐oxalato‐chromium(III)rubidium(I)]: a new supramolecular isomer

The title compound, [CrRb(C₂O₄)₂(H₂O)₂]_n, obtained under hydrothermal conditions and investigated structurally at 100 K, is a three‐dimensional supramolecular isomer of the layered structure compound studied at room temperature. This novel polymer is built up from crosslinked heterobimetallic units. The linkage of alternating edge‐ and vertex‐shared RbO₇(H₂O)₂ and CrO₄(H₂O)₂ polyhedra running along three different directions gives a dense packing. The two independent ligands display two η⁴‐chelation modes and two conventional carboxylate bridges. However, the pentadentate ligand connects the Cr^III and Rb^I ions through one O‐atom bridge, while the hexadentate ligand exhibits an additional η³‐chelation and two O‐atom bridges. Each coordinated water molecule forms an O‐atom bridge between the two metals. Moreover, in the absence of protonated ligands, these water molecules act as donors through their four H atoms in strong‐to‐weak hydrogen bonds. This results in zigzag chains of alternating oxalate and aqua ligands parallel to the twofold screw axis. The six double oxalates known to date containing an alkali and Cr^III all present layered two‐dimensional structures. In the series, this supramolecular isomer is the first three‐dimensional framework.