Abstract: | Dicarboxylate Groups as Ligands and Anions in Aquamagnesium Complexes: Crystal Structures of Mg (C4H2O4)(H2O)4] · H2O and Mg(H2O)6](C4HO4)2 · 2H2O ((C4H2O4)2— = Fumarate; (C4HO4)— = Hydrogenacetylenedicarboxylate) Crystals of tetraaqua(fumarato)magnesium‐hydrate ( 1 ) and hexaaquamagnesium‐bis(hydrogenacetylenedicarboxylate)‐dihydrate ( 2 ) were prepared by reacting MgCl2 with sodium fumarate and acetylenedicarboxylic acid, respectively. In 1 cis‐Mg(H2O)4 units are bridged by α, Ö‐bonded fumarate groups. The resulting zig zag chains exhibit the maximum symmetry compatible with space group symmetry C2/c. 2 consists of layers of voluminous Mg(H2O)6]2+ cations alternating with layers of C4HO4— anions. The nearly planar anions are held together by parallel stacking and by short hydrogen bonds. Both structures contain efficient H bridging systems. 1 : Space group C2/c, Z = 4, lattice constants at 20 °C: a = 5.298(1), b = 13.178(2), c = 13.374(2)Å; ß = 94.79(2)°, R1 = 0.024. 2 : Space group P1, Z = 1, lattice constants at 20 °C: a = 5.985(1), b = 6.515(1), c = 11.129(1)Å; α = 105.24(2), ß = 91.87(3), γ = 90.92(1)°, R1 = 0.034. |