NaYbP2O7 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(1), and two equivalent O(7) atoms. Yb(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form YbO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Yb(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-52°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent Yb(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-50°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Yb(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Yb(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Yb(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one Yb(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Yb(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Yb(1), and one P(1) atom.
NaYbP2O7 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(1), and two equivalent O(7) atoms. The Na(1)-O(2) bond length is 2.55 Å. The Na(1)-O(3) bond length is 2.48 Å. There is one shorter (2.51 Å) and one longer (2.75 Å) Na(1)-O(1) bond length. There is one shorter (2.52 Å) and one longer (2.65 Å) Na(1)-O(7) bond length. Yb(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form YbO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The Yb(1)-O(1) bond length is 2.36 Å. The Yb(1)-O(2) bond length is 2.34 Å. The Yb(1)-O(3) bond length is 2.33 Å. The Yb(1)-O(4) bond length is 2.25 Å. The Yb(1)-O(6) bond length is 2.29 Å. The Yb(1)-O(7) bond length is 2.35 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Yb(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 15-52°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.51 Å. The P(1)-O(5) bond length is 1.63 Å. The P(1)-O(7) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with three equivalent Yb(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-50°. The P(2)-O(2) bond length is 1.54 Å. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.63 Å. The P(2)-O(6) bond length is 1.52 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Yb(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Yb(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Yb(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one Yb(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Yb(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Yb(1), and one P(1) atom.