Labile Low-Valent Tin Azides: Syntheses, Structural Characterization, and Thermal Properties

The first two examples of the class of tetracoordinate low-valent, mixed-ligand tin azido complexes, Sn­(N₃)₂(L)₂, are shown to form upon reaction of SnCl₂ with NaN₃ and SnF₂ with Me₃SiN₃ in either pyridine or 4-picoline (2, L = py; 3, L = pic). These adducts of Sn­(N₃)₂ are shock- and friction-insensitive and stable at r.t. under an atmosphere of pyridine or picoline, respectively. A new, fast, and efficient method for the preparation of Sn­(N₃)₂ (1) directly from SnF₂, and by the stepwise de-coordination of py from 2 at r.t., is reported that yields 1 in microcrystalline form, permitting powder X-ray diffraction studies. Reaction of 1 with a nonbulky cationic H-bond donor forms the salt-like compound {C­(NH₂)₃}­Sn­(N₃)₃ (4) which is comparably stable despite its high nitrogen content (55%) and the absence of bulky weakly coordinating cations that are conventionally deemed essential in related systems of homoleptic azido metallates. The spectroscopic and crystallographic characterization of the polyazides 1–4 provides insight into azide-based H-bonded networks and unravels the previously unknown structure of 1 as an important lighter binary azide homologue of Pb­(N₃)₂. The atomic coordinates for 1 and 2–4 were derived from powder and single crystal XRD data, respectively; those for 1 are consistent with predictions made by DFT-D calculations under periodic boundary conditions.