Na5Ni2P2(CO7)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(12), one O(2), one O(3), one O(4), one O(7), and one O(9) atom to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Na(1)O7 pentagonal bipyramid,  an edgeedge with one P(2)O4 tetrahedra,  a faceface with one Ni(1)O6 octahedra, and  a faceface with one Na(1)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 65°. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(5), one O(6), one O(7), and one O(8) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(9), and two equivalent O(2) atoms. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(3), one O(5), one O(8), and two equivalent O(2) atoms to form NiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and faces with two equivalent Na(1)O7 pentagonal bipyramids. In the second Ni site, Ni(2) is bonded to one O(10), one O(4), one O(6), one O(9), and two equivalent O(7) atoms to form distorted NiO6 octahedra that share corners with two equivalent Na(1)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Na(1)O7 pentagonal bipyramids. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(12), and one O(8) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(10), one O(11), and one O(9) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(6), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra, and corners with two equivalent Na(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-50°. In the second P site, P(2) is bonded to one O(3), one O(4), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, corners with two equivalent Na(1)O7 pentagonal bipyramids, and edges with two equivalent Na(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-50°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(1), one Ni(1), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Ni(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ni(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Ni(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to two equivalent Na(2), one Ni(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ni(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal pyramidal geometry to two equivalent Na(2), one Ni(1), and one C(1) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(1), one Ni(2), and one C(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one Ni(2), and one C(2) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), two equivalent Na(2), and one C(2) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(3), two equivalent Na(1), and one C(1) atom.
Na5Ni2P2(CO7)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(12), one O(2), one O(3), one O(4), one O(7), and one O(9) atom to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Ni(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra,  an edgeedge with one Na(1)O7 pentagonal bipyramid,  an edgeedge with one P(2)O4 tetrahedra,  a faceface with one Ni(1)O6 octahedra, and  a faceface with one Na(1)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 65°. The Na(1)-O(1) bond length is 2.74 Å. The Na(1)-O(12) bond length is 2.32 Å. The Na(1)-O(2) bond length is 2.52 Å. The Na(1)-O(3) bond length is 2.32 Å. The Na(1)-O(4) bond length is 2.41 Å. The Na(1)-O(7) bond length is 2.77 Å. The Na(1)-O(9) bond length is 2.35 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(5), one O(6), one O(7), and one O(8) atom. The Na(2)-O(10) bond length is 2.55 Å. The Na(2)-O(11) bond length is 2.31 Å. The Na(2)-O(5) bond length is 2.59 Å. The Na(2)-O(6) bond length is 2.35 Å. The Na(2)-O(7) bond length is 2.42 Å. The Na(2)-O(8) bond length is 2.41 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(9), and two equivalent O(2) atoms. The Na(3)-O(1) bond length is 2.34 Å. The Na(3)-O(11) bond length is 2.39 Å. The Na(3)-O(12) bond length is 2.69 Å. The Na(3)-O(9) bond length is 2.68 Å. Both Na(3)-O(2) bond lengths are 2.43 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(3), one O(5), one O(8), and two equivalent O(2) atoms to form NiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and faces with two equivalent Na(1)O7 pentagonal bipyramids. The Ni(1)-O(1) bond length is 2.11 Å. The Ni(1)-O(3) bond length is 2.03 Å. The Ni(1)-O(5) bond length is 2.03 Å. The Ni(1)-O(8) bond length is 2.18 Å. Both Ni(1)-O(2) bond lengths are 2.10 Å. In the second Ni site, Ni(2) is bonded to one O(10), one O(4), one O(6), one O(9), and two equivalent O(7) atoms to form distorted NiO6 octahedra that share corners with two equivalent Na(1)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Na(1)O7 pentagonal bipyramids. The Ni(2)-O(10) bond length is 2.06 Å. The Ni(2)-O(4) bond length is 1.99 Å. The Ni(2)-O(6) bond length is 2.05 Å. The Ni(2)-O(9) bond length is 2.19 Å. Both Ni(2)-O(7) bond lengths are 2.07 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(1), one O(12), and one O(8) atom. The C(1)-O(1) bond length is 1.31 Å. The C(1)-O(12) bond length is 1.27 Å. The C(1)-O(8) bond length is 1.29 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(10), one O(11), and one O(9) atom. The C(2)-O(10) bond length is 1.30 Å. The C(2)-O(11) bond length is 1.27 Å. The C(2)-O(9) bond length is 1.30 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(5), one O(6), and two equivalent O(2) atoms to form PO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra, corners with three equivalent Ni(1)O6 octahedra, and corners with two equivalent Na(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-50°. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.54 Å. Both P(1)-O(2) bond lengths are 1.55 Å. In the second P site, P(2) is bonded to one O(3), one O(4), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, corners with two equivalent Na(1)O7 pentagonal bipyramids, and edges with two equivalent Na(1)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 40-50°. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(4) bond length is 1.58 Å. Both P(2)-O(7) bond lengths are 1.54 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(1), one Ni(1), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Ni(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ni(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Ni(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to two equivalent Na(2), one Ni(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ni(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal pyramidal geometry to two equivalent Na(2), one Ni(1), and one C(1) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(1), one Ni(2), and one C(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one Ni(2), and one C(2) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), two equivalent Na(2), and one C(2) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(3), two equivalent Na(1), and one C(1) atom.