Three-Dimensional Frameworks of Cubic (NH₄)₅Ga₄SbS₁₀, (NH₄)₄Ga₄SbS₉(OH)·H₂O, and (NH₄)₃Ga₄SbS₉(OH₂)·2H₂O

Three new isostructural open-framework sulfides, (NH₄)₅Ga₄SbS₁₀ (1), (NH₄)₄Ga₄SbS₉(OH)·H₂O (2a), and (NH₄)₃Ga₄SbS₉(H₂O)·2H₂O (2b), were synthesized under basic hydrothermal conditions using ammonium hydroxide as the structure-directing agent. The structures feature a three-dimensional open framework comprised of adamantane [Ga₄Q₁₀]⁸⁻ clusters linked with Sb³⁺ centers. The compounds are wide gap semiconductors, crystallize in the chiral space group P2₁3, and represent a new structure type. They exhibit nonlinear optical properties.