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 in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and two equivalent O(8) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(4), one O(5), one O(7), one O(8), and one O(9) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(2), one O(3), one O(6), and one O(7) atom. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(10), one O(11), one O(3), one O(5), and two equivalent O(7) atoms to form distorted NiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. In the second Ni site, Ni(2) is bonded to one O(12), one O(4), one O(6), one O(9), and two equivalent O(8) atoms to form distorted NiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. 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(3), and one O(5) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(6) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(9), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra and corners with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. In the second P site, P(2) is bonded to one O(10), one O(12), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra and corners with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(3), and one C(2) atom. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(3), one Ni(1), and one C(1) atom to form distorted edge-sharing ONa3NiC trigonal bipyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Ni(2), and one C(2) atom. In the fifth O site, O(5) is bonded to two equivalent Na(2), one Ni(1), and one C(1) atom to form distorted edge-sharing ONa2NiC trigonal pyramids. In the sixth O site, O(6) is bonded in a 1-coordinate geometry to one Na(1), two equivalent Na(3), one Ni(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ni(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ni(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to two equivalent Na(2), one Ni(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(3), one Ni(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Ni(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Ni(2), and one P(2) 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 in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and two equivalent O(8) atoms. The Na(1)-O(1) bond length is 2.52 Å. The Na(1)-O(2) bond length is 2.39 Å. The Na(1)-O(3) bond length is 2.41 Å. The Na(1)-O(6) bond length is 2.75 Å. Both Na(1)-O(8) bond lengths are 2.42 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(4), one O(5), one O(7), one O(8), and one O(9) atom. The Na(2)-O(1) bond length is 2.33 Å. The Na(2)-O(11) bond length is 2.51 Å. The Na(2)-O(4) bond length is 2.71 Å. The Na(2)-O(5) bond length is 2.34 Å. The Na(2)-O(7) bond length is 2.83 Å. The Na(2)-O(8) bond length is 2.58 Å. The Na(2)-O(9) bond length is 2.33 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(2), one O(3), one O(6), and one O(7) atom. The Na(3)-O(10) bond length is 2.34 Å. The Na(3)-O(12) bond length is 2.48 Å. The Na(3)-O(2) bond length is 2.37 Å. The Na(3)-O(3) bond length is 2.54 Å. The Na(3)-O(6) bond length is 2.43 Å. The Na(3)-O(7) bond length is 2.40 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(10), one O(11), one O(3), one O(5), and two equivalent O(7) atoms to form distorted NiO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra and corners with three equivalent P(1)O4 tetrahedra. The Ni(1)-O(10) bond length is 2.03 Å. The Ni(1)-O(11) bond length is 2.00 Å. The Ni(1)-O(3) bond length is 2.09 Å. The Ni(1)-O(5) bond length is 2.19 Å. Both Ni(1)-O(7) bond lengths are 2.08 Å. In the second Ni site, Ni(2) is bonded to one O(12), one O(4), one O(6), one O(9), and two equivalent O(8) atoms to form distorted NiO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The Ni(2)-O(12) bond length is 2.05 Å. The Ni(2)-O(4) bond length is 2.13 Å. The Ni(2)-O(6) bond length is 2.19 Å. The Ni(2)-O(9) bond length is 2.05 Å. Both Ni(2)-O(8) bond lengths are 2.10 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(3), and one O(5) atom. The C(1)-O(1) bond length is 1.27 Å. The C(1)-O(3) bond length is 1.32 Å. The C(1)-O(5) bond length is 1.29 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(6) atom. The C(2)-O(2) bond length is 1.28 Å. The C(2)-O(4) bond length is 1.29 Å. The C(2)-O(6) bond length is 1.31 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(9), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Ni(2)O6 octahedra and corners with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-51°. The P(1)-O(11) bond length is 1.57 Å. The P(1)-O(9) bond length is 1.55 Å. Both P(1)-O(7) bond lengths are 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(12), and two equivalent O(8) atoms to form PO4 tetrahedra that share  a cornercorner with one Ni(1)O6 octahedra and corners with three equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-51°. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(12) bond length is 1.57 Å. Both P(2)-O(8) bond lengths are 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), two equivalent Na(2), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(3), and one C(2) atom. In the third O site, O(3) is bonded to one Na(1), two equivalent Na(3), one Ni(1), and one C(1) atom to form distorted edge-sharing ONa3NiC trigonal bipyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Ni(2), and one C(2) atom. In the fifth O site, O(5) is bonded to two equivalent Na(2), one Ni(1), and one C(1) atom to form distorted edge-sharing ONa2NiC trigonal pyramids. In the sixth O site, O(6) is bonded in a 1-coordinate geometry to one Na(1), two equivalent Na(3), one Ni(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ni(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ni(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to two equivalent Na(2), one Ni(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(3), one Ni(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Ni(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Ni(2), and one P(2) atom.