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 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(10), and two equivalent O(7) atoms. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(11), one O(12), one O(7), one O(8), one O(9), and two equivalent O(10) atoms. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. In the second Ni site, Ni(2) is bonded to one O(11), one O(12), one O(8), one O(9), and two equivalent O(10) atoms to form NiO6 octahedra that share corners with four 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(2), one O(3), and one O(7) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(8), 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(4) atoms to form PO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-50°. In the second P site, P(2) is bonded to one O(11), one O(12), and two equivalent O(10) atoms to form PO4 tetrahedra that share corners with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-48°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Ni(1), and one C(1) atom. In the third O site, O(3) is bonded in a distorted trigonal bipyramidal geometry to one Na(2), two equivalent Na(1), one Ni(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ni(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Ni(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ni(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to two equivalent Na(2), two equivalent Na(3), and one C(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Ni(2), and one C(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal pyramidal geometry to two equivalent Na(3), one Ni(2), and one C(2) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(3), one Ni(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to two equivalent Na(3), one Ni(2), and one P(2) 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 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.33 Å. The Na(1)-O(2) bond length is 2.75 Å. The Na(1)-O(3) bond length is 2.39 Å. The Na(1)-O(5) bond length is 2.32 Å. The Na(1)-O(6) bond length is 2.45 Å. There is one shorter (2.47 Å) and one longer (2.86 Å) Na(1)-O(4) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(10), and two equivalent O(7) atoms. The Na(2)-O(2) bond length is 2.29 Å. The Na(2)-O(3) bond length is 2.59 Å. Both Na(2)-O(10) bond lengths are 2.44 Å. There is one shorter (2.41 Å) and one longer (2.79 Å) Na(2)-O(7) bond length. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(11), one O(12), one O(7), one O(8), one O(9), and two equivalent O(10) atoms. The Na(3)-O(11) bond length is 2.32 Å. The Na(3)-O(12) bond length is 2.51 Å. The Na(3)-O(7) bond length is 2.30 Å. The Na(3)-O(8) bond length is 2.70 Å. The Na(3)-O(9) bond length is 2.35 Å. There is one shorter (2.49 Å) and one longer (2.85 Å) Na(3)-O(10) bond length. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms to form NiO6 octahedra that share corners with four equivalent P(1)O4 tetrahedra. The Ni(1)-O(2) bond length is 2.11 Å. The Ni(1)-O(3) bond length is 2.20 Å. The Ni(1)-O(5) bond length is 2.05 Å. The Ni(1)-O(6) bond length is 2.03 Å. Both Ni(1)-O(4) bond lengths are 2.09 Å. In the second Ni site, Ni(2) is bonded to one O(11), one O(12), one O(8), one O(9), and two equivalent O(10) atoms to form NiO6 octahedra that share corners with four equivalent P(2)O4 tetrahedra. The Ni(2)-O(11) bond length is 2.03 Å. The Ni(2)-O(12) bond length is 2.01 Å. The Ni(2)-O(8) bond length is 2.09 Å. The Ni(2)-O(9) bond length is 2.11 Å. Both Ni(2)-O(10) 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(2), one O(3), and one O(7) atom. The C(1)-O(2) bond length is 1.30 Å. The C(1)-O(3) bond length is 1.30 Å. The C(1)-O(7) 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(8), and one O(9) atom. The C(2)-O(1) bond length is 1.26 Å. The C(2)-O(8) bond length is 1.30 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(4) atoms to form PO4 tetrahedra that share corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-50°. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(6) bond length is 1.57 Å. Both P(1)-O(4) bond lengths are 1.55 Å. In the second P site, P(2) is bonded to one O(11), one O(12), and two equivalent O(10) atoms to form PO4 tetrahedra that share corners with four equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-48°. The P(2)-O(11) bond length is 1.54 Å. The P(2)-O(12) bond length is 1.56 Å. Both P(2)-O(10) bond lengths are 1.55 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one C(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Ni(1), and one C(1) atom. In the third O site, O(3) is bonded in a distorted trigonal bipyramidal geometry to one Na(2), two equivalent Na(1), one Ni(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ni(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1), one Ni(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Ni(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to two equivalent Na(2), two equivalent Na(3), and one C(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to two equivalent Na(3), one Ni(2), and one C(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal pyramidal geometry to two equivalent Na(3), one Ni(2), and one C(2) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(3), one Ni(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to two equivalent Na(3), one Ni(2), and one P(2) 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.