Reported here is a unique crystalline semiconductor open framework material built from the large-sized supertetrahedral T4 and T5 clusters with the Mn-In-S compositions. The hybrid assembly between T4 and T5 clusters by sharing terminal mu(2)-S2- is for the first time observed among the cluster-based chalcogenide open frameworks. Such threedimensional structure displays non-interpenetrated diamond-type topology with extra-large nonframework volume of 82%. Moreover, ion exchange, CO2 adsorption, as well as photoluminescence properties of the title compound are also investigated.