Two new structures in the glycine-oxalic acid system

Glycinium semi-oxalate-II, C₂H₆NO₂ ⁺·C₂HO₄ ^-, (A), and diglycin-ium oxalate methanol disolvate, 2C₂H₆NO ₂ ⁺·C₂O₄ ^2-·2CH₃OH, (B), are new examples in the glycine-oxalic acid family. (A) is a new polymorph of the known glycinium semi-oxalate salt, (C). Compounds (A) and (C) have a similar packing of the semi-oxalate monoanions with respect to the glycinium cations, but in (A) the two glycinium cations and the two semi-oxalate anions in the asymmetric unit are non-equivalent, and the binding of the glycinium cations to each other is radically different. Based on this difference, one can expect that, although the two forms grow concomitantly from the same batch, a transformation between (A) and (C) in the solid state should be difficult. In (B), two glycinium cations and an oxalate anion, which sits across a centre of inversion, are linked via strong short O-H⋯O hydrogen bonds to form the main structural fragment, similar to that in diglycinium oxalate, (D). Methanol solvent mol-ecules are embedded between the glycinium cations of neighbouring fragments. These fragments form a three-dimensional network via N-H⋯O hydrogen bonds. Salts (B) and (D) can be obtained from the same solution by, respectively, slow or rapid anti-solvent crystallization.