Two-Dimensional Indium Sulfide Framework Constructed from Pentasupertetrahedral P1 and Supertetrahedral T2 Clusters

A new open-framework indium sulfide ([In<sub>12</sub>S<sub>24</sub>H<sub>2</sub>]<sup>10-</sup>) constructed from pentasupertetrahedral sulfide clusters ([In<sub>8</sub>S<sub>17</sub>H],- P1) and supertetrahedral sulfide clusters ([In<sub>4</sub>S<sub>10</sub>H],- T2) has been prepared through hydrothermal synthesis. Unlike previously reported P1 clusters that require divalent metal cations, the P1 cluster reported here consists of only trivalent ions (In<sup>3+</sup>) and is the only known example of tetrahedral clusters with a core sulfur site bonded to four trivalent ions. Each P1 cluster is joined to three T2 clusters (vice versa) to form an infinite two-dimensional sheet stacked along the crystallographic <i>c</i>-axis. In contrast with known three-dimensional open-framework indium sulfides in which locations of extraframework amines are rarely known due to disorder, structure-directing amine molecules are much less disordered as a result of host−guest N−H···S hydrogen bonding. The UV−vis diffuse reflectance spectrum shows that this material is a wide band gap semiconductor.