The newcrystalline compound, Lii2PO2N, was synthesized using high temperature solid state methods starting with a stoichiometric mixture of Li2O, P2O5,and P3N5. Its crystal structure was determined ab initio from powder X-ray diffraction. The compound crystallizes in the orthorhombic space group Cmc21 (# 36) with lattice constants a= 9.0692(4) Å, b=5.3999(2) Å, and c=4.6856(2) Å. The crystal structure of SD-Li2PO2N consists of parallel arrangements of anionic chains formed of corner sharing (PO2N2) tetrahedra. The chains are held together by Li+ cations. The structure of the synthesized material is similar to that predicted by Du and Holzwarth on the basis of first principles calculations (Phys. Rev. B 81, 184106 (2010)). The compound is chemically and structurally stable in air up to 600 oC and in vacuumup to 1050 oC. The Arrhenius activation energy of SD-Li2PO2N in pressed pellet formwas determined from electrochemical impedance spectroscopy measurements to be 0.6 eV, comparable to that of the glassy electrolyte LiPON developed at Oak Ridge National Laboratory. The minimum activation energies for Li ion vacancy and interstitial migrations are computed to be 0.4 eV and 0.8 eV, respectively. First principles calculations estimate the band gap of SD-Li2PO2N to be larger than 6 eV.