NaHoP2O7 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(6), and two equivalent O(7) atoms. Ho(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form HoO6 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(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent Ho(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-52°. In the second P site, P(2) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Ho(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-57°. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a distorted linear geometry to one Ho(1) and one P(2) atom. In the second O site, O(6) is bonded to two equivalent Na(1), one Ho(1), and one P(2) atom to form distorted corner-sharing ONa2HoP trigonal pyramids. In the third O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ho(1), and one P(2) atom. In the fourth O site, O(1) is bonded in a bent 150 degrees geometry to one Ho(1) and one P(1) atom. In the fifth O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ho(1), and one P(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Ho(1), and one P(1) atom. In the seventh O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom.
NaHoP2O7 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(6), and two equivalent O(7) atoms. The Na(1)-O(2) bond length is 2.45 Å. The Na(1)-O(3) bond length is 2.44 Å. There is one shorter (2.41 Å) and one longer (2.56 Å) Na(1)-O(6) bond length. There is one shorter (2.46 Å) and one longer (2.59 Å) Na(1)-O(7) bond length. Ho(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom to form HoO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The Ho(1)-O(1) bond length is 2.21 Å. The Ho(1)-O(2) bond length is 2.26 Å. The Ho(1)-O(3) bond length is 2.25 Å. The Ho(1)-O(5) bond length is 2.16 Å. The Ho(1)-O(6) bond length is 2.27 Å. The Ho(1)-O(7) bond length is 2.27 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent Ho(1)O6 octahedra and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-52°. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.61 Å. In the second P site, P(2) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Ho(1)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 16-57°. The P(2)-O(4) bond length is 1.60 Å. The P(2)-O(5) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.52 Å. The P(2)-O(7) bond length is 1.53 Å. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a distorted linear geometry to one Ho(1) and one P(2) atom. In the second O site, O(6) is bonded to two equivalent Na(1), one Ho(1), and one P(2) atom to form distorted corner-sharing ONa2HoP trigonal pyramids. In the third O site, O(7) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ho(1), and one P(2) atom. In the fourth O site, O(1) is bonded in a bent 150 degrees geometry to one Ho(1) and one P(1) atom. In the fifth O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Ho(1), and one P(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Ho(1), and one P(1) atom. In the seventh O site, O(4) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom.