Na5Ni2P2(CO7)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(13), one O(4), one O(5), one O(6), and one O(8) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(12), one O(2), one O(3), one O(4), one O(7), and one O(9) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(2), one O(6), and one O(8) atom. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(12), one O(13), one O(14), one O(2), and one O(8) atom. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(3), one O(5), 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(2), one O(3), one O(4), one O(5), one O(8), and one O(9) atom to form NiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. In the second Ni site, Ni(2) is bonded to one O(10), one O(12), one O(13), one O(14), one O(6), and one O(7) atom to form NiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two 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(11), one O(8), and one O(9) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(10), and one O(7) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(13), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra and corners with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-49°. In the second P site, P(2) is bonded to one O(14), one O(2), one O(3), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra and corners with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-49°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), and one C(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Na(4), one Ni(1), and one P(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Na(2), one Na(5), one Ni(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ni(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(5), one Ni(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Ni(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(5), one Ni(2), and one C(2) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one Ni(1), and one C(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Ni(1), and one C(1) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), 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), one Na(4), one Na(5), and one C(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Ni(2), and one P(1) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(4), one Ni(2), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(4), one Na(5), one Ni(2), and one P(2) atom.
Na5Ni2P2(CO7)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(13), one O(4), one O(5), one O(6), and one O(8) atom. The Na(1)-O(1) bond length is 2.31 Å. The Na(1)-O(10) bond length is 2.78 Å. The Na(1)-O(13) bond length is 2.31 Å. The Na(1)-O(4) bond length is 2.43 Å. The Na(1)-O(5) bond length is 2.78 Å. The Na(1)-O(6) bond length is 2.53 Å. The Na(1)-O(8) bond length is 2.36 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(12), one O(2), one O(3), one O(4), one O(7), and one O(9) atom. The Na(2)-O(1) bond length is 2.31 Å. The Na(2)-O(12) bond length is 2.83 Å. The Na(2)-O(2) bond length is 2.55 Å. The Na(2)-O(3) bond length is 2.34 Å. The Na(2)-O(4) bond length is 2.49 Å. The Na(2)-O(7) bond length is 2.33 Å. The Na(2)-O(9) bond length is 2.74 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(2), one O(6), and one O(8) atom. The Na(3)-O(1) bond length is 2.74 Å. The Na(3)-O(10) bond length is 2.30 Å. The Na(3)-O(11) bond length is 2.38 Å. The Na(3)-O(2) bond length is 2.41 Å. The Na(3)-O(6) bond length is 2.42 Å. The Na(3)-O(8) bond length is 2.67 Å. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(12), one O(13), one O(14), one O(2), and one O(8) atom. The Na(4)-O(10) bond length is 2.72 Å. The Na(4)-O(11) bond length is 2.32 Å. The Na(4)-O(12) bond length is 2.41 Å. The Na(4)-O(13) bond length is 2.31 Å. The Na(4)-O(14) bond length is 2.47 Å. The Na(4)-O(2) bond length is 2.90 Å. The Na(4)-O(8) bond length is 2.42 Å. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(3), one O(5), one O(7), and one O(9) atom. The Na(5)-O(11) bond length is 2.32 Å. The Na(5)-O(14) bond length is 2.55 Å. The Na(5)-O(3) bond length is 2.34 Å. The Na(5)-O(5) bond length is 2.43 Å. The Na(5)-O(7) bond length is 2.40 Å. The Na(5)-O(9) bond length is 2.66 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(8), and one O(9) atom to form NiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Ni(1)-O(2) bond length is 2.10 Å. The Ni(1)-O(3) bond length is 2.05 Å. The Ni(1)-O(4) bond length is 2.01 Å. The Ni(1)-O(5) bond length is 2.09 Å. The Ni(1)-O(8) bond length is 2.18 Å. The Ni(1)-O(9) bond length is 2.09 Å. In the second Ni site, Ni(2) is bonded to one O(10), one O(12), one O(13), one O(14), one O(6), and one O(7) atom to form NiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and corners with two equivalent P(2)O4 tetrahedra. The Ni(2)-O(10) bond length is 2.11 Å. The Ni(2)-O(12) bond length is 2.10 Å. The Ni(2)-O(13) bond length is 2.03 Å. The Ni(2)-O(14) bond length is 2.03 Å. The Ni(2)-O(6) bond length is 2.11 Å. The Ni(2)-O(7) bond length is 2.15 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(11), one O(8), and one O(9) atom. The C(1)-O(11) bond length is 1.28 Å. The C(1)-O(8) bond length is 1.31 Å. The C(1)-O(9) bond length is 1.29 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(10), and one O(7) atom. The C(2)-O(1) bond length is 1.27 Å. The C(2)-O(10) bond length is 1.31 Å. The C(2)-O(7) bond length is 1.30 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(12), one O(13), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra and corners with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-49°. The P(1)-O(12) bond length is 1.54 Å. The P(1)-O(13) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(14), one O(2), one O(3), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Ni(1)O6 octahedra and corners with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-49°. The P(2)-O(14) bond length is 1.56 Å. The P(2)-O(2) bond length is 1.56 Å. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.55 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(3), and one C(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Na(4), one Ni(1), and one P(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Na(2), one Na(5), one Ni(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ni(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(5), one Ni(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Ni(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(5), one Ni(2), and one C(2) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one Ni(1), and one C(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Ni(1), and one C(1) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), 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), one Na(4), one Na(5), and one C(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Ni(2), and one P(1) atom. In the thirteenth O site, O(13) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(4), one Ni(2), and one P(1) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(4), one Na(5), one Ni(2), and one P(2) atom.