Na5Fe2P2(CO7)2 crystallizes in the monoclinic P2_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(10), one O(2), one O(3), one O(5), 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(2), one O(4), one O(6), one O(7), and one O(8) atom. In the third Na site, Na(3) is bonded to one O(1), one O(10), one O(11), one O(13), one O(3), one O(5), 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(1)O4 tetrahedra,  an edgeedge with one Na(4)O7 pentagonal bipyramid,  an edgeedge with one P(2)O4 tetrahedra,  a faceface with one Fe(1)O6 octahedra, and  a faceface with one Na(4)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 60°. In the fourth Na site, Na(4) is bonded to one O(1), one O(11), one O(13), one O(3), one O(5), one O(7), and one O(9) atom to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Na(3)O7 pentagonal bipyramid,  an edgeedge with one P(2)O4 tetrahedra,  a faceface with one Fe(1)O6 octahedra, and  a faceface with one Na(3)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 62°. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(14), one O(2), one O(4), and one O(6) atom. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(11), one O(13), one O(3), one O(6), one O(7), 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,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a faceface with one Na(3)O7 pentagonal bipyramid, and  a faceface with one Na(4)O7 pentagonal bipyramid. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(14), one O(4), one O(5), and one O(9) atom. 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(4), and one O(5) atom. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(3), 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(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra, corners with two equivalent Na(3)O7 pentagonal bipyramids, and corners with two equivalent Na(4)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 39-45°. In the second P site, P(2) is bonded to one O(10), one O(12), one O(13), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  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 are 49°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(5), and one C(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(1), one Na(3), one Na(4), one Fe(1), and one C(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Fe(2), and one C(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(3), one Na(4), one Fe(2), and one C(1) atom to form a mixture of distorted corner and edge-sharing ONa3FeC trigonal bipyramids. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Fe(1), and one C(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Fe(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Fe(1), and one P(1) atom. In the ninth O site, O(9) is bonded to one Na(1), one Na(4), one Fe(2), and one P(2) atom to form a mixture of distorted corner and edge-sharing ONa2FeP trigonal pyramids. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one Fe(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Na(3), one Na(4), one Fe(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(5), one Fe(2), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Fe(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal non-coplanar geometry to one Na(5), one Fe(2), and one P(1) atom.
Na5Fe2P2(CO7)2 crystallizes in the monoclinic P2_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(10), one O(2), one O(3), one O(5), and one O(9) atom. The Na(1)-O(1) bond length is 2.54 Å. The Na(1)-O(10) bond length is 2.48 Å. The Na(1)-O(2) bond length is 2.74 Å. The Na(1)-O(3) bond length is 2.42 Å. The Na(1)-O(5) bond length is 2.56 Å. The Na(1)-O(9) bond length is 2.37 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. The Na(2)-O(1) bond length is 2.82 Å. The Na(2)-O(2) bond length is 2.43 Å. The Na(2)-O(4) bond length is 2.36 Å. The Na(2)-O(6) bond length is 2.67 Å. The Na(2)-O(7) bond length is 2.57 Å. The Na(2)-O(8) bond length is 2.58 Å. In the third Na site, Na(3) is bonded to one O(1), one O(10), one O(11), one O(13), one O(3), one O(5), 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(1)O4 tetrahedra,  an edgeedge with one Na(4)O7 pentagonal bipyramid,  an edgeedge with one P(2)O4 tetrahedra,  a faceface with one Fe(1)O6 octahedra, and  a faceface with one Na(4)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 60°. The Na(3)-O(1) bond length is 2.27 Å. The Na(3)-O(10) bond length is 2.74 Å. The Na(3)-O(11) bond length is 2.36 Å. The Na(3)-O(13) bond length is 2.50 Å. The Na(3)-O(3) bond length is 2.60 Å. The Na(3)-O(5) bond length is 2.39 Å. The Na(3)-O(8) bond length is 2.56 Å. In the fourth Na site, Na(4) is bonded to one O(1), one O(11), one O(13), one O(3), one O(5), one O(7), and one O(9) atom to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Na(3)O7 pentagonal bipyramid,  an edgeedge with one P(2)O4 tetrahedra,  a faceface with one Fe(1)O6 octahedra, and  a faceface with one Na(3)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 62°. The Na(4)-O(1) bond length is 2.27 Å. The Na(4)-O(11) bond length is 2.37 Å. The Na(4)-O(13) bond length is 2.57 Å. The Na(4)-O(3) bond length is 2.58 Å. The Na(4)-O(5) bond length is 2.41 Å. The Na(4)-O(7) bond length is 2.59 Å. The Na(4)-O(9) bond length is 2.53 Å. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(14), one O(2), one O(4), and one O(6) atom. The Na(5)-O(10) bond length is 2.54 Å. The Na(5)-O(12) bond length is 2.30 Å. The Na(5)-O(14) bond length is 2.47 Å. The Na(5)-O(2) bond length is 2.30 Å. The Na(5)-O(4) bond length is 2.65 Å. The Na(5)-O(6) bond length is 2.51 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(11), one O(13), one O(3), one O(6), one O(7), 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,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  a faceface with one Na(3)O7 pentagonal bipyramid, and  a faceface with one Na(4)O7 pentagonal bipyramid. The Fe(1)-O(11) bond length is 2.02 Å. The Fe(1)-O(13) bond length is 1.94 Å. The Fe(1)-O(3) bond length is 2.19 Å. The Fe(1)-O(6) bond length is 2.10 Å. The Fe(1)-O(7) bond length is 2.07 Å. The Fe(1)-O(8) bond length is 2.11 Å. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to one O(10), one O(12), one O(14), one O(4), one O(5), and one O(9) atom. The Fe(2)-O(10) bond length is 2.16 Å. The Fe(2)-O(12) bond length is 2.05 Å. The Fe(2)-O(14) bond length is 2.10 Å. The Fe(2)-O(4) bond length is 2.23 Å. The Fe(2)-O(5) bond length is 2.42 Å. The Fe(2)-O(9) bond length is 2.09 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(4), and one O(5) atom. The C(1)-O(1) bond length is 1.30 Å. The C(1)-O(4) bond length is 1.30 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(2), one O(3), and one O(6) atom. The C(2)-O(2) bond length is 1.26 Å. The C(2)-O(3) bond length is 1.32 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(7), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent Fe(1)O6 octahedra, corners with two equivalent Na(3)O7 pentagonal bipyramids, and corners with two equivalent Na(4)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 39-45°. The P(1)-O(11) bond length is 1.57 Å. The P(1)-O(14) bond length is 1.52 Å. The P(1)-O(7) bond length is 1.57 Å. The P(1)-O(8) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(10), one O(12), one O(13), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra,  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 are 49°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(12) bond length is 1.52 Å. The P(2)-O(13) bond length is 1.60 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 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Na(4), and one C(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(5), and one C(2) atom. In the third O site, O(3) is bonded in a distorted single-bond geometry to one Na(1), one Na(3), one Na(4), one Fe(1), and one C(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Fe(2), and one C(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(3), one Na(4), one Fe(2), and one C(1) atom to form a mixture of distorted corner and edge-sharing ONa3FeC trigonal bipyramids. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Fe(1), and one C(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), one Na(4), one Fe(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Fe(1), and one P(1) atom. In the ninth O site, O(9) is bonded to one Na(1), one Na(4), one Fe(2), and one P(2) atom to form a mixture of distorted corner and edge-sharing ONa2FeP trigonal pyramids. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one Fe(2), and one P(2) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Na(3), one Na(4), one Fe(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(5), one Fe(2), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Fe(1), and one P(2) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal non-coplanar geometry to one Na(5), one Fe(2), and one P(1) atom.