Solvothermal Synthesis of two 2‐D Thioantimonates(III) with Metal Complexes as Template Ions, [M(dap) 3 ]Sb 4 S 7 (M = Ni 2+ and Co 2+ )

Two new thioantimonates [M(dap) 3 ]Sb 4 S 7 (M = Ni 2+ ( 1 ) and Co 2+ ( 2 )) were synthesized under solvothermal conditions by the reaction of NiS (or Co metal), Sb and S in an aqueous solution of 1,2‐diaminopropane (dap). Compounds 1 and 2 are isostructural. The polymeric [Sb 4 S 7 2− ] n anion is composed of two SbS 3 trigonal pyramids and two SbS 4 units. The SbS 3 and SbS 4 units are interconnected by corners and edges to build a 2‐D puckered layer with Sb 4 S 4 and Sb 16 S 16 heterorings. The apertures of the large Sb 16 S 16 hetero‐rings are filled by two [M(dap) 3 ] 2+ complex cations which serve as template ions. The band gaps of 2.44 eV for 1 and 2.43 eV for 2 have been estimated from optical absorption spectra.