Abstract: | The title compound, Rb2Co(H2O)6](C8H5O4)4·4H2O, consists of nearly regular octahedral Co(H2O)6]2+ cations with the CoII cations on the inversion centre (special position 2a), Rb+ cations, hydrogen phthalate (Hpht−) anions and disordered water molecules. The Rb+ cation is surrounded by nine O atoms from Hpht− anions and water molecules, with a strongly deformed pentagonal–bipyramidal geometry and one apex split into three positions. The crystal packing is governed by numerous hydrogen bonds involving all water molecules and Hpht− anions. In this way, layers parallel to the ab plane are formed, with the aromatic rings of the Hpht− anions esentially directed along the c axis. While Hpht− anions form the outer part of the layers, disordered water molecules and Rb+ cations alternate with Co(H2O)6]2+ cations in the inner parts. The only interactions between the layers are van der Waals forces between the atoms of the aromatic rings. A search of the Cambridge Structural Database for coordination modes and types of hydrogen‐bonding interaction of the Hpht− anion showed that, when uncoordinated Hpht− anions are present, compounds with intermolecular hydrogen bonds are more numerous than compounds with intramolecular hydrogen bonds. For coordinated Hpht− anions, chelating and bridging anions are almost equally common, while monodentate anions are relatively scarce. The same coordination modes appear for Hpht− anions with or without intramolecular hydrogen bonds, although intramolecular hydrogen bonds are less common. |