Na5Fe2P2(CO7)2 crystallizes in the monoclinic Pc 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(12), one O(13), one O(4), one O(5), and two equivalent O(1) atoms. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(4) atoms. In the third Na site, Na(3) is bonded to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(10) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Na(3)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Na(4)O7 pentagonal bipyramid,  an edgeedge with one P(2)O4 tetrahedra,  a faceface with one Fe(2)O6 octahedra, and  a faceface with one Na(4)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 68°. In the fourth Na site, Na(4) is bonded to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(11) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Na(4)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Na(3)O7 pentagonal bipyramid,  an edgeedge with one P(2)O4 tetrahedra,  a faceface with one Fe(2)O6 octahedra, and  a faceface with one Na(3)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 65°. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), and two equivalent O(14) atoms. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form distorted FeO6 octahedra that share  a cornercorner with one Na(3)O7 pentagonal bipyramid,  a cornercorner with one Na(4)O7 pentagonal bipyramid, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In the second Fe site, Fe(2) is bonded to one O(10), one O(11), one O(12), one O(13), one O(7), and one O(9) atom to form distorted FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Na(3)O7 pentagonal bipyramid,  an edgeedge with one Na(4)O7 pentagonal bipyramid,  a faceface with one Na(3)O7 pentagonal bipyramid, and  a faceface with one Na(4)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(14), one O(2), and one O(3) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), 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(4), one O(5), one O(7), 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,  a cornercorner with one Na(3)O7 pentagonal bipyramid, and  a cornercorner with one Na(4)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 41-53°. In the second P site, P(2) is bonded to one O(10), one O(11), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Na(3)O7 pentagonal bipyramid,  a cornercorner with one Na(4)O7 pentagonal bipyramid,  an edgeedge with one Na(3)O7 pentagonal bipyramid, and  an edgeedge with one Na(4)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 33-46°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), 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(5), one Fe(1), and one C(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), 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(1), two equivalent Na(2), one Fe(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Fe(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Fe(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Na(2), one Fe(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Fe(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Na(3), one Na(4), one Fe(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(3), one Fe(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(4), one Fe(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal bipyramidal geometry to one Na(1), one Na(3), one Na(4), one Fe(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one Fe(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to one Na(3), one Na(4), two equivalent Na(5), and one C(1) atom.
Na5Fe2P2(CO7)2 crystallizes in the monoclinic Pc 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(12), one O(13), one O(4), one O(5), and two equivalent O(1) atoms. The Na(1)-O(12) bond length is 2.63 Å. The Na(1)-O(13) bond length is 2.41 Å. The Na(1)-O(4) bond length is 2.50 Å. The Na(1)-O(5) bond length is 2.40 Å. There is one shorter (2.50 Å) and one longer (2.78 Å) Na(1)-O(1) bond length. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(4) atoms. The Na(2)-O(1) bond length is 2.23 Å. The Na(2)-O(2) bond length is 2.63 Å. The Na(2)-O(3) bond length is 2.51 Å. The Na(2)-O(6) bond length is 2.37 Å. The Na(2)-O(7) bond length is 2.32 Å. There is one shorter (2.48 Å) and one longer (2.89 Å) Na(2)-O(4) bond length. In the third Na site, Na(3) is bonded to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(10) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Na(3)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Na(4)O7 pentagonal bipyramid,  an edgeedge with one P(2)O4 tetrahedra,  a faceface with one Fe(2)O6 octahedra, and  a faceface with one Na(4)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 68°. The Na(3)-O(12) bond length is 2.39 Å. The Na(3)-O(13) bond length is 2.58 Å. The Na(3)-O(14) bond length is 2.34 Å. The Na(3)-O(8) bond length is 2.67 Å. The Na(3)-O(9) bond length is 2.31 Å. There is one shorter (2.62 Å) and one longer (2.84 Å) Na(3)-O(10) bond length. In the fourth Na site, Na(4) is bonded to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(11) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Na(4)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Fe(2)O6 octahedra,  an edgeedge with one Na(3)O7 pentagonal bipyramid,  an edgeedge with one P(2)O4 tetrahedra,  a faceface with one Fe(2)O6 octahedra, and  a faceface with one Na(3)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 65°. The Na(4)-O(12) bond length is 2.38 Å. The Na(4)-O(13) bond length is 2.59 Å. The Na(4)-O(14) bond length is 2.37 Å. The Na(4)-O(8) bond length is 2.64 Å. The Na(4)-O(9) bond length is 2.30 Å. There is one shorter (2.64 Å) and one longer (2.80 Å) Na(4)-O(11) bond length. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(2), one O(3), and two equivalent O(14) atoms. The Na(5)-O(10) bond length is 2.61 Å. The Na(5)-O(11) bond length is 2.48 Å. The Na(5)-O(2) bond length is 2.36 Å. The Na(5)-O(3) bond length is 2.59 Å. There is one shorter (2.46 Å) and one longer (2.80 Å) Na(5)-O(14) bond length. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(8) atom to form distorted FeO6 octahedra that share  a cornercorner with one Na(3)O7 pentagonal bipyramid,  a cornercorner with one Na(4)O7 pentagonal bipyramid, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Fe(1)-O(2) bond length is 2.15 Å. The Fe(1)-O(3) bond length is 2.18 Å. The Fe(1)-O(4) bond length is 2.14 Å. The Fe(1)-O(5) bond length is 1.98 Å. The Fe(1)-O(6) bond length is 1.98 Å. The Fe(1)-O(8) bond length is 2.02 Å. In the second Fe site, Fe(2) is bonded to one O(10), one O(11), one O(12), one O(13), one O(7), and one O(9) atom to form distorted FeO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Na(3)O7 pentagonal bipyramid,  an edgeedge with one Na(4)O7 pentagonal bipyramid,  a faceface with one Na(3)O7 pentagonal bipyramid, and  a faceface with one Na(4)O7 pentagonal bipyramid. The Fe(2)-O(10) bond length is 2.08 Å. The Fe(2)-O(11) bond length is 2.10 Å. The Fe(2)-O(12) bond length is 2.29 Å. The Fe(2)-O(13) bond length is 2.24 Å. The Fe(2)-O(7) bond length is 2.07 Å. The Fe(2)-O(9) bond length is 2.13 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(14), one O(2), and one O(3) atom. The C(1)-O(14) bond length is 1.29 Å. The C(1)-O(2) bond length is 1.31 Å. The C(1)-O(3) 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(12), and one O(13) atom. The C(2)-O(1) bond length is 1.27 Å. The C(2)-O(12) bond length is 1.31 Å. The C(2)-O(13) bond length is 1.32 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(4), one O(5), one O(7), 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,  a cornercorner with one Na(3)O7 pentagonal bipyramid, and  a cornercorner with one Na(4)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 41-53°. The P(1)-O(4) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.57 Å. The P(1)-O(7) bond length is 1.54 Å. The P(1)-O(9) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(10), one O(11), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra,  a cornercorner with one Na(3)O7 pentagonal bipyramid,  a cornercorner with one Na(4)O7 pentagonal bipyramid,  an edgeedge with one Na(3)O7 pentagonal bipyramid, and  an edgeedge with one Na(4)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 33-46°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(11) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.58 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), 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(5), one Fe(1), and one C(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), 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(1), two equivalent Na(2), one Fe(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Fe(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Fe(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Na(2), one Fe(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Fe(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Na(3), one Na(4), one Fe(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(3), one Fe(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(5), two equivalent Na(4), one Fe(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal bipyramidal geometry to one Na(1), one Na(3), one Na(4), one Fe(2), and one C(2) atom. In the thirteenth O site, O(13) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(4), one Fe(2), and one C(2) atom. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to one Na(3), one Na(4), two equivalent Na(5), and one C(1) atom.