Structural characterization of sodium and potassium 3-nitrohydrogenphthalate coordination polymers

Abstract

Abstract The synthesis, crystal structures and properties of two alkali metal 3-nitrohydrogenphthalates obtained by a 1:2 reaction of M2CO3 (M = K or Na) with 3-nitrophthalic acid (LH2) are reported. In the anhydrous potassium coordination polymer [K(LH)] (LH = 2-carboxy-3-nitrobenzoate) 1, the K+ cation is bonded to nine oxygen atoms from six symmetry related (LH)– ligands resulting in a distorted {KO9} coordination polyhedron. Five of the six oxygen atoms including a nitro oxygen atom of the crystallographically unique 2-carboxy-3-nitrobenzoate are involved in metal binding. The μ6-bridging mode of (LH)– places the K+ cations into the layers of the two-dimensional (2D) coordination polymer. Each {KO9} polyhedron in 1 shares edges with two other polyhedra along the b and c axes. A low temperature structure redetermination of [Na(L#H)(H2O)3]·H2O (L#H = 2-carboxy-6-nitrobenzoate) 2 has revealed that the (L#H)− anion is bonded to the Na+ cation in a monodentate fashion via the carbonyl oxygen atom of the –COOH group and two of the three unique aqua ligands exhibit a bridging bidentate mode stabilizing a chain polymer. The structure of compound 2 thus consists of chains of edge-sharing {NaO6} octahedra. Thermal decomposition of 1 or 2 results in the formation of metal carbonate residues.