Single crystals of three novel transition-metal oxalates, dirubidium diaquadioxalatocobalt(II) dihydrate or dirubidium cobalt(II) bis(oxalate) tetrahydrate, Rb2[Co(C2O4)2(H2O)2]·2H2O, (I), catena-poly[dirubidium [[dichloridocobalt(II)]-μ-oxalato]] or dirubidium cobalt(II) dichloride oxalate, {Rb2[CoCl2(C2O4)]}
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, (II), and poly[dipotassium [tri-μ-oxalato-copper(II)dilithium] dihydrate] or dipotassium dilithium copper(II) tris(oxalate) dihydrate, {K2[Li2Cu(C2O4)3]·2H2O}
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, (III), have been grown under hydrothermal conditions and their crystal structures determined using single-crystal X-ray diffraction. The structure of (I) exhibits isolated octahedral [Co(C2O4)2(H2O)2] units, whereas (II) consists of trans chains of Co2+ ions bridged by bidentate oxalato ligands and (III) displays a novel tri-periodic network of Li+ and Cu2+ ions linked by oxalato bridging ligands.