Single crystals of two new bimetallic oxalate compounds with the formula [ACr(C2O4)2(H2O)4]n (A = Li or Na), namely catena-poly[[diaqualithium(I)]-μ-oxalato-κ4O1,O2:O1',O2'-[diaquachromium(III)]-μ-oxalato-κ4O1,O2:O1',O2'], (I), and catena-poly[[diaquasodium(I)]-μ-oxalato-κ4O1,O2:O1',O2'-[di-aquachromium(III)]-μ-oxalato-κ4O1,O2:O1',O2'], (II), have been synthesized, characterized and their crystal structures elucidated by X-ray diffraction analysis and compared. The compounds crystallize in the monoclinic space group C2/m for (I) and in the triclinic space group P-1 for (II); however, they have somewhat similar features. In the asymmetric unit of (I), the Li and Cr atoms both have space-group-imposed 2/m site symmetry, while only half of the oxalate ligand is present and two independent water molecules lie on the mirror plane. The water O atoms around the Li atom are disordered over two equivalent positions separated by 0.54 (4) Å. In the asymmetric unit of (II), the atoms of one C2O42- ligand and two independent water molecules are in general positions, and the Na and Cr atoms lie on an inversion centre. Taking into account the symmetry sites of both metallic elements, the unit cells may be described as pseudo-face-centred monoclinic for (I) and as pseudo-centred triclinic for (II). Both crystal structures are comprised of one-dimensional chains of alternating trans-Cr(CO)4(H2O)2 and trans-A(CO)4(H2O)2 units μ2-bridged by bis-chelating oxalate ligands. The resulting linear chains are parallel to the [101] direction for (I) and to the [11-1] direction for (II). Within the two coordination polymers, strong hydrogen bonds result in tetrameric R44(12) synthons which link the metal chains, thus leading to two-dimensaional supramolecular architectures. The two structures differ from each other with respect to the symmetry relations inside the ligand, the role of electrostatic forces in the crystal structure and the molecular interactions of the hydrogen-bonded networks. Moreover, they exhibit the same UV-Vis pattern typical of a CrIII centrosymmetric geometry, while the IR absorption shows some differences due to the oxalate-ligand conformation. Polymers (I) and (II) are also distinguished by a different behaviours during the decomposition process, the precursor (I) leading to the oxide LiCrO2, while the residues of (II) consist of a mixture of sodium carbonate and CrIII oxide.
Keywords: crystal structure; lithium; low dimensionality; one-dimensional coordination polymer; sodium; two-dimensional framework.