The reaction of Cr(NO 3 ) 3 •9H 2 O with sodium cyclobutane-1,1-dicarboxylate Na 2 (cbdc) was studied and the conditions for the formation and crystallization of Na I —Cr III carboxylate complexes in various media were found. The synthesis in water followed by the use of EtOH as a crystallization medium enables the isolation of the compound {Na 3 Cr(cbdc) 3 (EtOH) 2 (H 2 O)•H 2 O} n ( 1 ). The 2D polymeric structure of this compound is composed of mononuclear Cr(cbdc) 3 3− units. The similar recrystallization from MeOH leads to the formation of the 2D polymer CaNa 2 Cr 2 (cbdc) 4 (H 2 O) 4 (OMe) 2 (MeOH) 2 n ( 2 ) containing binuclear Cr 2 (cbdc) 4 (μ-OMe) 2 4− units. A similar reaction in water in the presence of an excess of NaOH followed by the recrystallization from MeOH afforded crystals of the compounds {Na 4 Cr 2 (cbdc) 4 (H 2 O) 4 (OH)(OMe)•H 2 O} n ( 3 ) and {Na 4 Cr 2 (cbdc) 4 (H 2 O) 3 (MeOH)(OH)(OMe)•H 2 O} n ( 4 ) having similar 1D-polymeric structures. The reaction of Cr(NO 3 ) 3 •9 H 2 O with Na 2 (cbdc) in MeOH followed by the benzene vapor diffusion into the reaction solution gave crystals of the compound {Na 3 Cr(cbdc) 3 (MeOH) 2 •0.5C 6 H 6 } n ( 5 ) having a 2D polymeric structure similar to that of compound 1 .