One-dimensional oxalato-bridged heterobimetallic coordination polymers by using [the [Cr(pyim)(C2O4)2]− complex as metalloligand [pyim = 2-(2′-pyridyl)imidazole]

Abstract

Abstract Four new coordination polymers based on the use of the [Cr(pyim)(C2O4)2]− species as a metalloligand, namely [LiCr(pyim)(C2O4)2(MeOH)]n (1), {[CaCr2(pyim)2(C2O4)4]·2MeOH}n (2), {[SrCr2(pyim)2(C2O4)4(H2O)]·0.45MeOH·4.55H2O}n (3) and {[CdCr2(pyim)2(C2O4)4]·MeOH}n (4) [pyim\u202f=\u202f2-(2′-pyridyl)imidazole] have been synthesized and characterized by elemental analyses, IR spectra and X-ray diffraction on single crystals. Complex 1 is a neutral heterobimetallic chain where the tris(chelated) chromium(III) unit acts as a bis-bidentate ligand towards {Li(MeOH)}+ fragments through its two oxalate ligands, each lithium ion being five-coordinate in a intermediate surrounding between square pyramidal and trigonal bipyramidal. The structure of 2 consists of neutral oxalato-bridged chromium(III)-calcium(II) double chains of single chirality [all the tris(chelated) chromium centres have the same chirality either Λ or λ] and methanol molecules of crystallization. Each calcium ion in 2 exhibits a square antiprism environment which is built by four bidentate oxalate ligands from four [Cr(pyim)(C2O4)2]− units. Neutral oxalato-bridged chromium(III)-strontium(II) double chains also occur in 3 with methanol and water molecules of crystallization, each alkaline-earth cation being nine-coordinate in a monocapped square antiprism environment which is defined by a water molecule and eight oxalate-oxygens from four [Cr(pyim)(C2O4)2]− units. The CrIII2MII2 loops [M\u202f=\u202fCa (2) and Sr (3)] within each double chain are planar. The structure of 4 is also made of neutral oxalato-bridged chromium(III)-cadmium(II) double chains but in contrast to 2 and 3, the chirality of the tris(chelated) chromium unit in 4 is alternated in each loop and the adjacent CrIII2CdII2 loops are not planar but form a dihedral angle of 84.8°. The potential use of the [Cr(pyim)(C2O4)2]− entity as a metalloligand in designing heterobimetallic compounds is analyzed and discussed.