Tetraorganopnictonium and Alkali Metal Salts of Pyridine‐2,6‐di‐tetrazolate

Alkali metal (Na, K) and tetraorganopnictonium (AsPh4, PPh4) salts were prepared from 2,6-bis(1H-tetrazol-5-yl)pyridine (H2pydtz) and characterized by multinuclear NMR, IR, and UV/Vis absorption spectroscopy. Single crystal XRD of (AsPh4)2(pydtz)·5H2O reveals isolated pydtz2– dianions sandwiched between two AsPh4+ cations and an interesting hydrogen bridging network comprising the five co-crystallized water molecules and the three pydtz N atoms. (PPh4)2(pydtz)·5H2O is isostructural to (AsPh4)2(pydtz)·5H2O as revealed from powder XRD measurements and corresponding Rietveld fits. The crystal structure of the mixed salt Na3(PPh4)(pydtz)2·12H2O reveals π-stacking interaction of the pydtz2–, a polymeric chain of water molecules and Na+ cations in an extended hydrogen bonding and Na+-coordinating network. PPh4+ cations interact solely through their positive charge. The alkali metal salts were soluble in water, alcohols, and DMF, whereas the pnictonium salts were additionally soluble in less polar solvents such as acetone, DMSO, CH2Cl2, or THF.