Na3Ni2P2(CO7)2 crystallizes in the monoclinic P2_1 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(11), one O(14), one O(3), one O(4), and one O(5) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(13), one O(6), one O(7), and one O(8) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(13), one O(2), one O(6), one O(7), and one O(9) atom. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(4), and one O(6) atom to form 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(11), one O(12), one O(5), one O(7), one O(8), and one O(9) atom to form 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(10), and one O(14) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(11), one O(12), and one O(13) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(6), and one O(7) atom 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 40-49°. In the second P site, P(2) is bonded to one O(4), one O(5), one O(8), and one O(9) atom 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 41-49°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Ni(1), and one C(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(3), one Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Ni(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Ni(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Ni(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ni(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Na(2), one Na(3), one Ni(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(2), one Ni(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(3), one Ni(2), and one P(2) atom. In the tenth O site, O(10) is bonded to one Na(2), one Na(3), one Ni(1), and one C(1) atom to form distorted edge-sharing ONa2NiC trigonal pyramids. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(1), one Ni(2), and one C(2) atom. In the twelfth O site, O(12) is bonded to one Na(2), one Na(3), one Ni(2), and one C(2) atom to form distorted edge-sharing ONa2NiC trigonal pyramids. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one C(2) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one C(1) atom.
Na3Ni2P2(CO7)2 crystallizes in the monoclinic P2_1 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(11), one O(14), one O(3), one O(4), and one O(5) atom. The Na(1)-O(1) bond length is 2.61 Å. The Na(1)-O(11) bond length is 2.43 Å. The Na(1)-O(14) bond length is 2.26 Å. The Na(1)-O(3) bond length is 2.39 Å. The Na(1)-O(4) bond length is 2.44 Å. The Na(1)-O(5) bond length is 2.55 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(13), one O(6), one O(7), and one O(8) atom. The Na(2)-O(10) bond length is 2.31 Å. The Na(2)-O(12) bond length is 2.51 Å. The Na(2)-O(13) bond length is 2.32 Å. The Na(2)-O(6) bond length is 2.61 Å. The Na(2)-O(7) bond length is 2.39 Å. The Na(2)-O(8) bond length is 2.38 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(13), one O(2), one O(6), one O(7), and one O(9) atom. The Na(3)-O(10) bond length is 2.32 Å. The Na(3)-O(12) bond length is 2.51 Å. The Na(3)-O(13) bond length is 2.32 Å. The Na(3)-O(2) bond length is 2.80 Å. The Na(3)-O(6) bond length is 2.64 Å. The Na(3)-O(7) bond length is 2.40 Å. The Na(3)-O(9) bond length is 2.42 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(4), and one O(6) atom to form 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(1) bond length is 2.04 Å. The Ni(1)-O(10) bond length is 2.04 Å. The Ni(1)-O(2) bond length is 2.02 Å. The Ni(1)-O(3) bond length is 2.07 Å. The Ni(1)-O(4) bond length is 1.95 Å. The Ni(1)-O(6) bond length is 2.00 Å. In the second Ni site, Ni(2) is bonded to one O(11), one O(12), one O(5), one O(7), one O(8), and one O(9) atom to form 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(11) bond length is 2.04 Å. The Ni(2)-O(12) bond length is 2.04 Å. The Ni(2)-O(5) bond length is 1.95 Å. The Ni(2)-O(7) bond length is 2.03 Å. The Ni(2)-O(8) bond length is 2.05 Å. The Ni(2)-O(9) bond length is 2.04 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(10), and one O(14) atom. The C(1)-O(1) bond length is 1.29 Å. The C(1)-O(10) bond length is 1.32 Å. The C(1)-O(14) bond length is 1.25 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(11), one O(12), and one O(13) atom. The C(2)-O(11) bond length is 1.30 Å. The C(2)-O(12) bond length is 1.31 Å. The C(2)-O(13) bond length is 1.26 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(6), and one O(7) atom 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 40-49°. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.57 Å. The P(1)-O(7) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(4), one O(5), one O(8), and one O(9) atom 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 41-49°. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.55 Å. The P(2)-O(9) bond length is 1.55 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Ni(1), and one C(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(3), one Ni(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Ni(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Ni(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Ni(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Ni(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Na(2), one Na(3), one Ni(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(2), one Ni(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(3), one Ni(2), and one P(2) atom. In the tenth O site, O(10) is bonded to one Na(2), one Na(3), one Ni(1), and one C(1) atom to form distorted edge-sharing ONa2NiC trigonal pyramids. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(1), one Ni(2), and one C(2) atom. In the twelfth O site, O(12) is bonded to one Na(2), one Na(3), one Ni(2), and one C(2) atom to form distorted edge-sharing ONa2NiC trigonal pyramids. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one C(2) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one C(1) atom.