NaLi2PO4 is Aluminum carbonitride-derived structured and crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. P(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with eight equivalent Li(1)O4 tetrahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Li(1), and one P(1) atom to form distorted ONa2Li2P trigonal bipyramids that share corners with two equivalent O(1)Na2Li2P trigonal bipyramids, corners with six equivalent O(2)NaLi2P trigonal pyramids, and edges with two equivalent O(2)NaLi2P trigonal pyramids. In the second O site, O(2) is bonded to one Na(1), two equivalent Li(1), and one P(1) atom to form distorted ONaLi2P trigonal pyramids that share corners with three equivalent O(1)Na2Li2P trigonal bipyramids, corners with four equivalent O(2)NaLi2P trigonal pyramids, and  an edgeedge with one O(1)Na2Li2P trigonal bipyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Li(1), and one P(1) atom.
NaLi2PO4 is Aluminum carbonitride-derived structured and crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms. There is one shorter (2.54 Å) and one longer (2.59 Å) Na(1)-O(1) bond length. Both Na(1)-O(2) bond lengths are 2.30 Å. There is one shorter (2.43 Å) and one longer (2.82 Å) Na(1)-O(3) bond length. Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with four equivalent Li(1)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(3) bond length is 2.00 Å. There is one shorter (1.98 Å) and one longer (2.00 Å) Li(1)-O(2) bond length. P(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with eight equivalent Li(1)O4 tetrahedra. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.56 Å. Both P(1)-O(2) bond lengths are 1.56 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Li(1), and one P(1) atom to form distorted ONa2Li2P trigonal bipyramids that share corners with two equivalent O(1)Na2Li2P trigonal bipyramids, corners with six equivalent O(2)NaLi2P trigonal pyramids, and edges with two equivalent O(2)NaLi2P trigonal pyramids. In the second O site, O(2) is bonded to one Na(1), two equivalent Li(1), and one P(1) atom to form distorted ONaLi2P trigonal pyramids that share corners with three equivalent O(1)Na2Li2P trigonal bipyramids, corners with four equivalent O(2)NaLi2P trigonal pyramids, and  an edgeedge with one O(1)Na2Li2P trigonal bipyramid. In the third O site, O(3) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Li(1), and one P(1) atom.