Two‐dimensional coordination polymeric structures in caesium complexes with ring‐substituted phenoxyacetic acids

The two‐dimensional polymeric structures of the caesium complexes with the phenoxyacetic acid analogues (4‐fluorophenoxy)acetic acid, (3‐chloro‐2‐methylphenoxy)acetic acid and the herbicidally active (2,4‐dichlorophenoxy)acetic acid (2,4‐D), namely polyμ₅‐(4‐fluorophenoxy)acetato]μ₄‐(4‐fluorophenoxy)acetato]dicaesium], Cs₂(C₈H₆FO₃)₂]_n, (I), polyaquaμ₅‐(3‐chloro‐2‐methylphenoxy)acetato]caesium], Cs(C₉H₈ClO₃)(H₂O)]_n, (II), and polyμ₇‐(2,4‐dichlorophenoxy)acetato](2,4‐dichlorphenoxy)acetic acid]caesium], Cs(C₈H₅Cl₂O₃)(C₈H₆Cl₂O₃)]_n, (III), are described. In (I), the Cs⁺ cations of the two individual irregular coordination polyhedra in the asymmetric unit (one CsO₇ and the other CsO₈) are linked by bridging carboxylate O‐atom donors from the two ligand molecules, both of which are involved in bidentate chelate O_carboxy,O_phenoxy interactions, while only one has a bidentate carboxylate O,O′‐chelate interaction. Polymeric extension is achieved through a number of carboxylate O‐atom bridges, with a minimum Cs...Cs separation of 4.3231 (9) Å, giving layers which lie parallel to (001). In hydrated complex (II), the irregular nine‐coordination about the Cs⁺ cation comprises a single monodentate water molecule, a bidentate O_carboxy,O_phenoxy chelate interaction and six bridging carboxylate O‐atom bonding interactions, giving a Cs...Cs separation of 4.2473 (3) Å. The water molecule forms intralayer hydrogen bonds within the two‐dimensional layers, which lie parallel to (100). In complex (III), the irregular centrosymmetric CsO₆Cl₂ coordination environment comprises two O‐atom donors and two ring‐substituted Cl‐atom donors from two hydrogen bis(2,4‐dichlorophenoxy)acetate] ligand species in a bidentate chelate mode, and four O‐atom donors from bridging carboxyl groups. The duplex ligand species lie across crystallographic inversion centres, linked through a short O—H...O hydrogen bond involving the single acid H atom. Structure extension gives layers which lie parallel to (001). The present set of structures of Cs salts of phenoxyacetic acids show previously demonstrated trends among the alkali metal salts of simple benzoic acids with no stereochemically favourable interactive substituent groups for formation of two‐dimensional coordination polymers.