Na5Fe2P2(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 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(8), and one O(9) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(5), and one O(7) atom. In the third Na site, Na(3) is bonded to one O(1), one O(10), one O(12), one O(14), one O(3), one O(6), and one O(8) atom to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 67°. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(14), one O(4), one O(5), one O(7), and one O(9) atom. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(2), one O(3), one O(6), one O(7), and one O(9) atom. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(10), one O(12), one O(14), one O(3), one O(5), and one O(9) atom to form distorted FeO6 octahedra that share  a cornercorner with one Na(3)O7 pentagonal bipyramid, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a faceface with one Na(3)O7 pentagonal bipyramid. In the second Fe site, Fe(2) is bonded to one O(11), one O(13), one O(4), one O(6), one O(7), and one O(8) atom to form distorted FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Na(3)O7 pentagonal bipyramid. 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(5) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), 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(14), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and  an edgeedge with one Na(3)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 39-51°. In the second P site, P(2) is bonded to one O(10), one O(12), one O(13), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Na(3)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 39-45°. 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), one Na(4), and one C(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(5), and one C(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one Fe(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Fe(2), and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one Fe(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Na(5), one Fe(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one Fe(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Fe(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Na(1), one Na(4), one Na(5), one Fe(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Fe(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(4), one Fe(2), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(5), one Fe(1), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(5), one Fe(2), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Fe(1), and one P(1) atom.
Na5Fe2P2(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 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(8), and one O(9) atom. The Na(1)-O(1) bond length is 2.55 Å. The Na(1)-O(2) bond length is 2.60 Å. The Na(1)-O(3) bond length is 2.32 Å. The Na(1)-O(6) bond length is 2.74 Å. The Na(1)-O(8) bond length is 2.47 Å. The Na(1)-O(9) bond length is 2.39 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(2), one O(4), one O(5), and one O(7) atom. The Na(2)-O(1) bond length is 2.93 Å. The Na(2)-O(10) bond length is 2.41 Å. The Na(2)-O(2) bond length is 2.43 Å. The Na(2)-O(4) bond length is 2.47 Å. The Na(2)-O(5) bond length is 2.45 Å. The Na(2)-O(7) bond length is 2.74 Å. In the third Na site, Na(3) is bonded to one O(1), one O(10), one O(12), one O(14), one O(3), one O(6), and one O(8) atom to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 67°. The Na(3)-O(1) bond length is 2.35 Å. The Na(3)-O(10) bond length is 2.55 Å. The Na(3)-O(12) bond length is 2.33 Å. The Na(3)-O(14) bond length is 2.53 Å. The Na(3)-O(3) bond length is 2.52 Å. The Na(3)-O(6) bond length is 2.46 Å. The Na(3)-O(8) bond length is 2.80 Å. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(14), one O(4), one O(5), one O(7), and one O(9) atom. The Na(4)-O(1) bond length is 2.38 Å. The Na(4)-O(11) bond length is 2.38 Å. The Na(4)-O(14) bond length is 2.50 Å. The Na(4)-O(4) bond length is 2.55 Å. The Na(4)-O(5) bond length is 2.36 Å. The Na(4)-O(7) bond length is 2.65 Å. The Na(4)-O(9) bond length is 2.84 Å. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(2), one O(3), one O(6), one O(7), and one O(9) atom. The Na(5)-O(12) bond length is 2.34 Å. The Na(5)-O(13) bond length is 2.46 Å. The Na(5)-O(2) bond length is 2.23 Å. The Na(5)-O(3) bond length is 2.70 Å. The Na(5)-O(6) bond length is 2.53 Å. The Na(5)-O(7) bond length is 2.83 Å. The Na(5)-O(9) bond length is 2.46 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(10), one O(12), one O(14), one O(3), one O(5), and one O(9) atom to form distorted FeO6 octahedra that share  a cornercorner with one Na(3)O7 pentagonal bipyramid, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a faceface with one Na(3)O7 pentagonal bipyramid. The Fe(1)-O(10) bond length is 2.17 Å. The Fe(1)-O(12) bond length is 2.07 Å. The Fe(1)-O(14) bond length is 2.09 Å. The Fe(1)-O(3) bond length is 2.23 Å. The Fe(1)-O(5) bond length is 2.22 Å. The Fe(1)-O(9) bond length is 2.24 Å. In the second Fe site, Fe(2) is bonded to one O(11), one O(13), one O(4), one O(6), one O(7), and one O(8) atom to form distorted FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one Na(3)O7 pentagonal bipyramid. The Fe(2)-O(11) bond length is 1.97 Å. The Fe(2)-O(13) bond length is 1.99 Å. The Fe(2)-O(4) bond length is 2.17 Å. The Fe(2)-O(6) bond length is 2.25 Å. The Fe(2)-O(7) bond length is 2.06 Å. The Fe(2)-O(8) bond length is 2.00 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(5) atom. The C(1)-O(2) bond length is 1.28 Å. The C(1)-O(3) bond length is 1.32 Å. The C(1)-O(5) bond length is 1.30 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(4), and one O(6) atom. The C(2)-O(1) bond length is 1.28 Å. The C(2)-O(4) bond length is 1.30 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(14), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and  an edgeedge with one Na(3)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 39-51°. The P(1)-O(11) bond length is 1.56 Å. The P(1)-O(14) bond length is 1.55 Å. The P(1)-O(8) bond length is 1.57 Å. The P(1)-O(9) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(12), one O(13), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, and corners with two equivalent Na(3)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 39-45°. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(12) bond length is 1.54 Å. The P(2)-O(13) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.57 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), one Na(4), and one C(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(5), and one C(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one Fe(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Fe(2), and one C(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one Fe(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Na(5), one Fe(2), and one C(2) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one Fe(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Fe(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a 1-coordinate geometry to one Na(1), one Na(4), one Na(5), one Fe(1), and one P(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Fe(1), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(4), one Fe(2), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(3), one Na(5), one Fe(1), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Na(5), one Fe(2), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Fe(1), and one P(1) atom.