Self-assembled metal chalcogenide open-framework materials such as that shown in the Figure-a projection on the [100] plane of the structure of a microporous layered tin(IV) sulfide (DABCOH)(2)Sn3S7 (1), where DABCOH denotes singly protonated 1,8-diazabicyclooctane - are of interest for chemical sensing applications. A "very soft chemistry", room temperature synthesis of 1 is reported.