Neutron diffraction study of lithium hydrogen phthalate monohydrate: A material with two very short intramolecular O⋅⋅⋅H⋅⋅⋅O hydrogen bonds

Abstract

The structure of lithium hydrogen phthalate monohydrate has been refined based upon neutron diffraction data obtained at three temperatures: 15, 100, and 298 K. All bond distances have been determined with precision better than 0.002 Å. The two crystallographically independent hydrogen phthalate anions in the unit cell both possess very short intramolecular O⋅⋅⋅H⋅⋅⋅O hydrogen bonds with O⋅⋅⋅O≊2.4 Å and ∠O⋅⋅⋅H⋅⋅⋅O≊170°. One of these linkages is very decidedly asymmetric, with O⋅⋅⋅H=1.122(1) Å and H⋅⋅⋅O=1.294(1) Å at 15 K, reflecting the fact that the two O atoms have quite different environments in the crystal. The second O⋅⋅⋅H⋅⋅⋅O bond is more nearly symmetric, with O⋅⋅⋅H=1.195(1) Å and H⋅⋅⋅O=1.205(1) Å at 15 K, but the difference between the two distances is still significant. The asymmetry of the short hydrogen bonds appears somewhat more pronounced at 298 K than at the lower temperatures. A corresponding shift with temperature of the H atom in the short intramolecular hydrogen bond was found previously in 2,3‐pyridinedicarboxylic acid, which has a molecular geometry similar to that found here.