Gerty T. and Carl F. Cori discovered, during research on the metabolism of sugars in organisms, the important role of the phosphate ester of a simple sugar. Glucose molecules are released from glycogen-the glucose stored in the liver-in the presence of phosphates and enter the blood as α-D-glucose-1-phosphate (Glc-1PH2). Currently, the crystal structure of three phosphates, Glc-1PNa2·3.5·H2O, Glc-1PK2·2H2O, and Glc-1PHK, is known. Research has shown that reactions of Glc-1PH2 with carbonates produce new complexes with ammonium ions [Glc-1P(NH4)2·3H2O] and mixed complexes: potassium-sodium and ammonium-sodium [Glc-1P(X)1.5Na0.5·4H2O; X = K or NH4]. The crystallization of dicationic complexes has been carried out in aqueous systems containing equimolar amounts of cations (1:1; X-Na). It was found that the first fractions of crystalline complexes always had cations in the ratio 3/2:1/2. The second batch of crystals obtained from the remaining mother liquid consisted either of the previously studied Na+, K+ or NH4+ complexes, or it was a new sodium hydrate-Glc-1PNa2·5·H2O. The isolated ammonium-potassium complex shows an isomorphic cation substitution and a completely unique composition: Glc-1PH(NH4)xK1-x (x = 0.67). The Glc-1P2- ligand has chelating fragments and/or bridging atoms, and complexes containing one type of cation show different modes of coordinating oxygen atoms with cations. However, in the case of the potassium-sodium and ammonium-sodium structures, high structural similarities are observed. The 1D and 2D NMR spectra showed that the conformation of Glc-1P2- is rigid in solution as in the solid state, where only rotations of the phosphate group around the C-O-P bonds are observed.