The cation and anion bonding modes make a difference: an unprecedented layered structure and a tri(hetero)nuclear...

Mixing solutions of M²⁺ (M = Cu²⁺ or Zn²⁺) salts containing cyclam (cyclam = 1,4,8,11-tetraazacyclotetradecane) as the ligand and an aqueous solution of Na₃SbS₄·9H₂O at room temperature led to the crystallization of two new compounds within minutes: {[Cu(cyclam)]₃[SbS₄]₂}·20nH₂O (I) and {[Zn(cyclam)]₃[SbS₄]₂}·8H₂O (II). In the structure of I [SbS₄]^3- anions acting as a tridentate ligand join CuN₄S₂ octahedra generating twelve-membered rings by corner-sharing of SbS₄ and CuN₄S₂ units. The rings are condensed into layers, which are stacked onto each other in a 6R polytype manner. The layers contain large pores with the water molecules located between the layers above and below the pores. In contrast, the structure of II comprises a discrete molecular tri(hetero)nuclear moiety with a bidentate [SbS₄]^3- anion connecting two rectangular pyramidal ZnN₄S polyhedra. The crystal water molecules of I and II can be thermally removed, and I and II are recovered by treatment under a humid atmosphere. The EPR spectrum of I indicates the presence of Cu²⁺ cations, which is unusual in the environment of S^2- anions. The different bonding situations and the preferences for the coordination geometries of Cu²⁺ and Zn²⁺ cations are rationalized by DFT based calculations, demonstrating that Cu²⁺ prefers an octahedral environment while Zn²⁺ adopts the square-pyramidal coordination. The pronounced differences in the vibrational spectra are also analyzed with DFT, showing how the different modes are influenced by the differing bond strengths.