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(4), one O(5), one O(7), and one O(8) 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(3), one O(6), and one O(9) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(13), one O(4), one O(5), one O(7), and one O(9) atom. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(12), one O(14), one O(2), one O(3), one O(6), one O(7), and one O(9) atom. In the fifth Na site, Na(5) is bonded to one O(10), one O(12), one O(14), one O(2), one O(3), one O(6), and one O(8) atom to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(2)O6 octahedra,  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 P(2)O4 tetrahedra, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 68°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(13), one O(3), one O(5), one O(7), and one O(8) atom to form distorted FeO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  a faceface with one Na(5)O7 pentagonal bipyramid. In the second Fe site, Fe(2) is bonded to one O(10), one O(11), one O(14), one O(4), one O(6), and one O(9) atom to form distorted FeO6 octahedra that share  a cornercorner with one Na(5)O7 pentagonal bipyramid,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Na(5)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(1), 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(2), 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(13), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, and  a cornercorner with one Na(5)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 38-50°. In the second P site, P(2) is bonded to one O(10), one O(12), one O(14), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra,  a cornercorner with one Na(5)O7 pentagonal bipyramid, and  an edgeedge with one Na(5)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 37-46°. 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(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(4), one Na(5), and one C(2) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), 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), one Na(3), one Fe(2), and one C(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Fe(1), and one C(1) atom. In the sixth O site, O(6) is bonded to one Na(2), one Na(4), one Na(5), one Fe(2), and one C(2) atom to form a mixture of distorted edge and corner-sharing ONa3FeC trigonal bipyramids. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), 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(1), one Na(5), one Fe(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Fe(2), and one P(2) atom. In the tenth O site, O(10) is bonded to one Na(2), one Na(5), one Fe(2), and one P(2) atom to form a mixture of distorted edge and corner-sharing ONa2FeP trigonal pyramids. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(3), one Fe(2), and one P(1) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Na(4), one Na(5), one Fe(1), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Na(3), one Fe(1), 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 Fe(2), and one P(2) 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(4), one O(5), one O(7), and one O(8) atom. The Na(1)-O(1) bond length is 2.45 Å. The Na(1)-O(2) bond length is 2.93 Å. The Na(1)-O(4) bond length is 2.35 Å. The Na(1)-O(5) bond length is 2.70 Å. The Na(1)-O(7) bond length is 2.61 Å. The Na(1)-O(8) bond length is 2.50 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(3), one O(6), and one O(9) atom. The Na(2)-O(1) bond length is 2.68 Å. The Na(2)-O(10) bond length is 2.42 Å. The Na(2)-O(2) bond length is 2.52 Å. The Na(2)-O(3) bond length is 2.44 Å. The Na(2)-O(6) bond length is 2.56 Å. The Na(2)-O(9) bond length is 2.50 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(13), one O(4), one O(5), one O(7), and one O(9) atom. The Na(3)-O(1) bond length is 2.30 Å. The Na(3)-O(11) bond length is 2.32 Å. The Na(3)-O(13) bond length is 2.51 Å. The Na(3)-O(4) bond length is 2.63 Å. The Na(3)-O(5) bond length is 2.45 Å. The Na(3)-O(7) bond length is 2.86 Å. The Na(3)-O(9) bond length is 2.46 Å. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(12), one O(14), one O(2), one O(3), one O(6), one O(7), and one O(9) atom. The Na(4)-O(12) bond length is 2.38 Å. The Na(4)-O(14) bond length is 2.46 Å. The Na(4)-O(2) bond length is 2.29 Å. The Na(4)-O(3) bond length is 2.61 Å. The Na(4)-O(6) bond length is 2.43 Å. The Na(4)-O(7) bond length is 2.67 Å. The Na(4)-O(9) bond length is 2.83 Å. In the fifth Na site, Na(5) is bonded to one O(10), one O(12), one O(14), one O(2), one O(3), one O(6), and one O(8) atom to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(2)O6 octahedra,  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 P(2)O4 tetrahedra, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 68°. The Na(5)-O(10) bond length is 2.62 Å. The Na(5)-O(12) bond length is 2.36 Å. The Na(5)-O(14) bond length is 2.52 Å. The Na(5)-O(2) bond length is 2.28 Å. The Na(5)-O(3) bond length is 2.63 Å. The Na(5)-O(6) bond length is 2.44 Å. The Na(5)-O(8) bond length is 2.71 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(12), one O(13), one O(3), one O(5), one O(7), and one O(8) atom to form distorted FeO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  a faceface with one Na(5)O7 pentagonal bipyramid. The Fe(1)-O(12) bond length is 2.03 Å. The Fe(1)-O(13) bond length is 1.95 Å. The Fe(1)-O(3) bond length is 2.17 Å. The Fe(1)-O(5) bond length is 2.12 Å. The Fe(1)-O(7) bond length is 2.12 Å. The Fe(1)-O(8) bond length is 2.05 Å. In the second Fe site, Fe(2) is bonded to one O(10), one O(11), one O(14), one O(4), one O(6), and one O(9) atom to form distorted FeO6 octahedra that share  a cornercorner with one Na(5)O7 pentagonal bipyramid,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Na(5)O7 pentagonal bipyramid. The Fe(2)-O(10) bond length is 2.05 Å. The Fe(2)-O(11) bond length is 2.07 Å. The Fe(2)-O(14) bond length is 2.16 Å. The Fe(2)-O(4) bond length is 2.23 Å. The Fe(2)-O(6) bond length is 2.35 Å. The Fe(2)-O(9) bond length is 2.11 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(3), and one O(5) atom. The C(1)-O(1) bond length is 1.27 Å. The C(1)-O(3) bond length is 1.32 Å. The C(1)-O(5) bond length is 1.31 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(6) atom. The C(2)-O(2) bond length is 1.29 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(13), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, and  a cornercorner with one Na(5)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 38-50°. The P(1)-O(11) bond length is 1.52 Å. The P(1)-O(13) bond length is 1.57 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(14), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O6 octahedra, corners with three equivalent Fe(2)O6 octahedra,  a cornercorner with one Na(5)O7 pentagonal bipyramid, and  an edgeedge with one Na(5)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 37-46°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(12) bond length is 1.58 Å. The P(2)-O(14) bond length is 1.55 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 4-coordinate geometry to one Na(1), one Na(2), one Na(3), 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(4), one Na(5), and one C(2) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), 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), one Na(3), one Fe(2), and one C(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Fe(1), and one C(1) atom. In the sixth O site, O(6) is bonded to one Na(2), one Na(4), one Na(5), one Fe(2), and one C(2) atom to form a mixture of distorted edge and corner-sharing ONa3FeC trigonal bipyramids. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), 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(1), one Na(5), one Fe(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Fe(2), and one P(2) atom. In the tenth O site, O(10) is bonded to one Na(2), one Na(5), one Fe(2), and one P(2) atom to form a mixture of distorted edge and corner-sharing ONa2FeP trigonal pyramids. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(3), one Fe(2), and one P(1) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Na(4), one Na(5), one Fe(1), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Na(3), one Fe(1), 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 Fe(2), and one P(2) atom.