Crystal structure of a water oxidation catalyst solvate with composition (NH(4))(2)[Fe(IV)(L-6H)]·3CH(3)COOH (L = clathrochelate ligand).

The synthetic availability of mol-ecular water oxidation catalysts containing high-valent ions of 3d metals in the active site is a prerequisite to enabling photo- and electrochemical water splitting on a large scale. Herein, the synthesis and crystal structure of di-ammonium {μ-1,3,4,7,8,10,12,13,16,17,19,22-dodeca-aza-tetra-cyclo-[8.8.4.1(3,17).1(8,12)]tetra-cosane-5,6,14,15,20,21-hexa-onato}ferrate(IV) acetic acid tris-olvate, (NH(4))(2)[Fe(IV)(C(12)H(12)N(12)O(6))]·3CH(3)COOH or (NH(4))(2)[Fe(IV)(L-6H)]·3CH(3)COOH is reported. The Fe(IV) ion is encapsulated by the macropolycyclic ligand, which can be described as a dodeca-aza-quadricyclic cage with two capping tri-aza-cyclo-hexane fragments making three five- and six six-membered alternating chelate rings with the central Fe(IV) ion. The local coord-ination environment of Fe(IV) is formed by six deprotonated hydrazide nitro-gen atoms, which stabilize the unusual oxidation state. The Fe(IV) ion lies on a twofold rotation axis (multiplicity 4, Wyckoff letter e) of the space group C2/c. Its coordination geometry is inter-mediate between a trigonal prism (distortion angle φ = 0°) and an anti-prism (φ = 60°) with φ = 31.1°. The Fe-N bond lengths lie in the range 1.9376†(13)-1.9617†(13)†à , as expected for tetra-valent iron. Structure analysis revealed that three acetic acid mol-ecules additionally co-crystallize per one iron(IV) complex, and one of them is positionally disordered over four positions. In the crystal structure, the ammonium cations, complex dianions and acetic acid mol-ecules are inter-connected by an intricate system of hydrogen bonds, mainly via the oxamide oxygen atoms acting as acceptors.