Na5LiFe2P2(CO7)2 crystallizes in the triclinic P1 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 to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(5) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Na(2)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 P(1)O4 tetrahedra, and  a faceface with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 71°. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(10) atoms. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(11) atoms. 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. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(6), and one O(7) atom. There are two inequivalent Fe sites. In the first Fe site, Fe(1) 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  a cornercorner with one Na(2)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(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 corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Na(2)O7 pentagonal bipyramid, and  a faceface with one Na(2)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(2)O7 pentagonal bipyramid, and  an edgeedge with one Na(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 41-59°. 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, and  a cornercorner with one Na(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 41-57°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Li(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(2), and one C(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Na(2), one Na(5), one Li(1), one Fe(2), and one C(1) atom. In the fourth O site, O(4) is bonded to one Na(1), one Li(1), one Fe(2), and one P(1) atom to form distorted ONaLiFeP trigonal pyramids that share  a cornercorner with one O(8)Na2FeP tetrahedra, corners with two equivalent O(7)NaLiFeP tetrahedra,  a cornercorner with one O(12)Na3FeC trigonal bipyramid, and  an edgeedge with one O(6)NaLiFeP trigonal pyramid. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), two equivalent Na(2), one Fe(2), and one P(1) atom. In the sixth O site, O(6) is bonded to one Na(2), one Li(1), one Fe(2), and one P(2) atom to form distorted ONaLiFeP trigonal pyramids that share corners with two equivalent O(8)Na2FeP tetrahedra, corners with two equivalent O(7)NaLiFeP tetrahedra, and  an edgeedge with one O(4)NaLiFeP trigonal pyramid. In the seventh O site, O(7) is bonded to one Na(2), one Li(1), one Fe(1), and one P(1) atom to form distorted ONaLiFeP tetrahedra that share  a cornercorner with one O(12)Na3FeC trigonal bipyramid, corners with two equivalent O(4)NaLiFeP trigonal pyramids, and corners with two equivalent O(6)NaLiFeP trigonal pyramids. In the eighth O site, O(8) is bonded to one Na(3), one Na(4), one Fe(2), and one P(2) atom to form distorted ONa2FeP tetrahedra that share corners with two equivalent O(12)Na3FeC trigonal bipyramids,  a cornercorner with one O(4)NaLiFeP trigonal pyramid, and corners with two equivalent O(6)NaLiFeP trigonal pyramids. 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(1), 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(1), 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(1), and one P(2) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Na(3), one Na(4), one Fe(1), and one C(2) atom to form distorted ONa3FeC trigonal bipyramids that share  a cornercorner with one O(7)NaLiFeP tetrahedra, corners with two equivalent O(8)Na2FeP tetrahedra, and  a cornercorner with one O(4)NaLiFeP trigonal pyramid. 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(1), 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.
Na5LiFe2P2(CO7)2 crystallizes in the triclinic P1 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 2.47 Å. The Na(1)-O(13) bond length is 2.34 Å. The Na(1)-O(4) bond length is 2.40 Å. The Na(1)-O(5) bond length is 2.52 Å. There is one shorter (2.51 Å) and one longer (2.71 Å) Na(1)-O(1) bond length. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and two equivalent O(5) atoms to form distorted NaO7 pentagonal bipyramids that share  a cornercorner with one Fe(1)O6 octahedra, corners with two equivalent Na(2)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 P(1)O4 tetrahedra, and  a faceface with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 71°. The Na(2)-O(1) bond length is 2.37 Å. The Na(2)-O(2) bond length is 2.61 Å. The Na(2)-O(3) bond length is 2.45 Å. The Na(2)-O(6) bond length is 2.35 Å. The Na(2)-O(7) bond length is 2.51 Å. There is one shorter (2.58 Å) and one longer (2.79 Å) Na(2)-O(5) bond length. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(10) atoms. The Na(3)-O(12) bond length is 2.45 Å. The Na(3)-O(13) bond length is 2.65 Å. The Na(3)-O(14) bond length is 2.29 Å. The Na(3)-O(8) bond length is 2.42 Å. The Na(3)-O(9) bond length is 2.30 Å. There is one shorter (2.53 Å) and one longer (2.88 Å) Na(3)-O(10) bond length. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(12), one O(13), one O(14), one O(8), one O(9), and two equivalent O(11) atoms. The Na(4)-O(12) bond length is 2.45 Å. The Na(4)-O(13) bond length is 2.65 Å. The Na(4)-O(14) bond length is 2.30 Å. The Na(4)-O(8) bond length is 2.42 Å. The Na(4)-O(9) bond length is 2.30 Å. There is one shorter (2.54 Å) and one longer (2.84 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 2.60 Å. The Na(5)-O(11) bond length is 2.43 Å. The Na(5)-O(2) bond length is 2.32 Å. The Na(5)-O(3) bond length is 2.53 Å. There is one shorter (2.42 Å) and one longer (2.80 Å) Na(5)-O(14) bond length. Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(6), and one O(7) atom. The Li(1)-O(1) bond length is 2.21 Å. The Li(1)-O(3) bond length is 2.60 Å. The Li(1)-O(4) bond length is 2.16 Å. The Li(1)-O(6) bond length is 2.12 Å. The Li(1)-O(7) bond length is 2.10 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) 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  a cornercorner with one Na(2)O7 pentagonal bipyramid, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Fe(1)-O(10) bond length is 2.09 Å. The Fe(1)-O(11) bond length is 2.09 Å. The Fe(1)-O(12) bond length is 2.42 Å. The Fe(1)-O(13) bond length is 2.26 Å. The Fe(1)-O(7) bond length is 2.17 Å. The Fe(1)-O(9) bond length is 2.15 Å. In the second Fe site, Fe(2) 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 corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Na(2)O7 pentagonal bipyramid, and  a faceface with one Na(2)O7 pentagonal bipyramid. The Fe(2)-O(2) bond length is 2.23 Å. The Fe(2)-O(3) bond length is 2.31 Å. The Fe(2)-O(4) bond length is 2.11 Å. The Fe(2)-O(5) bond length is 2.11 Å. The Fe(2)-O(6) bond length is 2.17 Å. The Fe(2)-O(8) 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(14), one O(2), and one O(3) atom. The C(1)-O(14) bond length is 1.30 Å. The C(1)-O(2) bond length is 1.30 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 1.30 Å. The C(2)-O(12) bond length is 1.30 Å. The C(2)-O(13) bond length is 1.31 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(2)O7 pentagonal bipyramid, and  an edgeedge with one Na(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 41-59°. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(7) 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(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, and  a cornercorner with one Na(2)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles range from 41-57°. The P(2)-O(10) bond length is 1.56 Å. The P(2)-O(11) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.56 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Li(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(2), and one C(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Na(2), one Na(5), one Li(1), one Fe(2), and one C(1) atom. In the fourth O site, O(4) is bonded to one Na(1), one Li(1), one Fe(2), and one P(1) atom to form distorted ONaLiFeP trigonal pyramids that share  a cornercorner with one O(8)Na2FeP tetrahedra, corners with two equivalent O(7)NaLiFeP tetrahedra,  a cornercorner with one O(12)Na3FeC trigonal bipyramid, and  an edgeedge with one O(6)NaLiFeP trigonal pyramid. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), two equivalent Na(2), one Fe(2), and one P(1) atom. In the sixth O site, O(6) is bonded to one Na(2), one Li(1), one Fe(2), and one P(2) atom to form distorted ONaLiFeP trigonal pyramids that share corners with two equivalent O(8)Na2FeP tetrahedra, corners with two equivalent O(7)NaLiFeP tetrahedra, and  an edgeedge with one O(4)NaLiFeP trigonal pyramid. In the seventh O site, O(7) is bonded to one Na(2), one Li(1), one Fe(1), and one P(1) atom to form distorted ONaLiFeP tetrahedra that share  a cornercorner with one O(12)Na3FeC trigonal bipyramid, corners with two equivalent O(4)NaLiFeP trigonal pyramids, and corners with two equivalent O(6)NaLiFeP trigonal pyramids. In the eighth O site, O(8) is bonded to one Na(3), one Na(4), one Fe(2), and one P(2) atom to form distorted ONa2FeP tetrahedra that share corners with two equivalent O(12)Na3FeC trigonal bipyramids,  a cornercorner with one O(4)NaLiFeP trigonal pyramid, and corners with two equivalent O(6)NaLiFeP trigonal pyramids. 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(1), 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(1), 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(1), and one P(2) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Na(3), one Na(4), one Fe(1), and one C(2) atom to form distorted ONa3FeC trigonal bipyramids that share  a cornercorner with one O(7)NaLiFeP tetrahedra, corners with two equivalent O(8)Na2FeP tetrahedra, and  a cornercorner with one O(4)NaLiFeP trigonal pyramid. 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(1), 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.