The designed construction of inorganic solid-state materials from distinct and soluble molecular components presents one of the greatest ongoing challenges facing modern synthetic chemistry.1 Recent attempts toutilize thisapproach for the preparation of three-dimensional network solids using inorganic molecular precursors have resulted in oligomeric productsZ and noncrystalline materials.' The current level of understanding of such chemical syntheses and how to effectively control the atomic structure and thecrystallinity of the product is~eryrudimentary.~ To investigate and understand the factors affecting such processes, we have begun to examine the chemistry of linking cage structures into three-dimensional networks, using main-group molecular cages as initial objects. We report here the synthesis and structure of an extended microporous sulfide network, MnGe4Slo.2(CH3)4N, obtained in crystalline form by the addition copolymerization of Mn(I1) with the cage compound, Ge4SI0[(CH3)4N]4, a t room temperature. In a digestion bomb, GeS25 (0.50 g, 3.7 mmol) and 2 mL of a 2 M aqueous solution of (CH3)4NHS were added to 8 mL of an aqueous solution that had been saturated with HzS. This mixture was heated at 150 "C for 3 days, and the resulting slightly yellowish solution was allowed to stand in an open container. After 24 h, cube-shaped colorless crystals of GedSlo[ (CH3)4N]d6 were obtained (0.45 g) in 54% yield. This compound is air stable and can be solubilized in water. The tetraethyland the tetrapropylammonium salts are prepared similarly, and they are found to have good solubility in most polar organic solvents, such as acetonitrile, N,N-dimethylformamide, and 1,2-dichloroethane. Single crystal structural analysis70n G ~ ~ S I O [ ( C H ~ ) ~ N ] ~ shows the presence of discrete (CH3)4N+ cations and Ge4Slo6 anions, which possess an adamantane-like structure, shown in Figure 1.