Na5LiFe2P2(CO7)2 crystallizes in the monoclinic Pm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(7), one O(8), and one O(9) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(12), and two equivalent O(9) atoms. Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(11), and two equivalent O(4) 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(5), one O(7), and two equivalent O(4) atoms to form distorted FeO6 octahedra that share 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 in a 5-coordinate geometry to one O(10), one O(6), one O(8), and two equivalent O(9) atoms. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(12), 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(10), and one O(11) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(6), one O(8), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. In the second P site, P(2) is bonded to one O(5), one O(7), and two equivalent O(9) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one Li(1), and one C(2) atom to form distorted corner-sharing ONa2LiC tetrahedra. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(1), one Fe(1), and one C(1) atom. In the third O site, O(3) is bonded to one Na(3), two equivalent Na(1), one Fe(1), and one C(1) atom to form distorted ONa3FeC trigonal bipyramids that share  a cornercorner with one O(7)Na2FeP tetrahedra and corners with two equivalent O(1)Na2LiC tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Li(1), one Fe(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Fe(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Fe(2), and one P(1) atom. In the seventh O site, O(7) is bonded to two equivalent Na(2), one Fe(1), and one P(2) atom to form distorted corner-sharing ONa2FeP tetrahedra. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to two equivalent Na(2), one Fe(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Fe(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one Fe(2), and one C(2) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one C(2) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to two equivalent Na(2), two equivalent Na(3), and one C(1) atom.
Na5LiFe2P2(CO7)2 crystallizes in the monoclinic Pm space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.35 Å. The Na(1)-O(2) bond length is 2.74 Å. The Na(1)-O(3) bond length is 2.39 Å. The Na(1)-O(5) bond length is 2.34 Å. The Na(1)-O(6) bond length is 2.44 Å. There is one shorter (2.48 Å) and one longer (2.88 Å) Na(1)-O(4) bond length. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(10), one O(12), one O(7), one O(8), and one O(9) atom. The Na(2)-O(10) bond length is 2.41 Å. The Na(2)-O(12) bond length is 2.31 Å. The Na(2)-O(7) bond length is 2.44 Å. The Na(2)-O(8) bond length is 2.35 Å. The Na(2)-O(9) bond length is 2.46 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(2), one O(3), two equivalent O(12), and two equivalent O(9) atoms. The Na(3)-O(2) bond length is 2.28 Å. The Na(3)-O(3) bond length is 2.60 Å. There is one shorter (2.43 Å) and one longer (2.80 Å) Na(3)-O(12) bond length. Both Na(3)-O(9) bond lengths are 2.46 Å. Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(11), and two equivalent O(4) atoms. The Li(1)-O(1) bond length is 2.03 Å. The Li(1)-O(11) bond length is 2.09 Å. Both Li(1)-O(4) bond lengths are 2.22 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(2), one O(3), one O(5), one O(7), and two equivalent O(4) atoms to form distorted FeO6 octahedra that share 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 2.21 Å. The Fe(1)-O(3) bond length is 2.30 Å. The Fe(1)-O(5) bond length is 2.14 Å. The Fe(1)-O(7) bond length is 2.12 Å. Both Fe(1)-O(4) bond lengths are 2.14 Å. In the second Fe site, Fe(2) is bonded in a 5-coordinate geometry to one O(10), one O(6), one O(8), and two equivalent O(9) atoms. The Fe(2)-O(10) bond length is 2.14 Å. The Fe(2)-O(6) bond length is 2.11 Å. The Fe(2)-O(8) bond length is 2.15 Å. Both Fe(2)-O(9) bond lengths are 2.12 Å. There are two inequivalent C sites. In the first C site, C(1) is bonded in a trigonal planar geometry to one O(12), one O(2), and one O(3) atom. The C(1)-O(12) bond length is 1.29 Å. The C(1)-O(2) bond length is 1.30 Å. The C(1)-O(3) bond length is 1.31 Å. In the second C site, C(2) is bonded in a trigonal planar geometry to one O(1), one O(10), and one O(11) atom. The C(2)-O(1) bond length is 1.30 Å. The C(2)-O(10) bond length is 1.31 Å. The C(2)-O(11) bond length is 1.30 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(6), one O(8), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. The P(1)-O(6) bond length is 1.56 Å. The P(1)-O(8) bond length is 1.55 Å. Both P(1)-O(4) bond lengths are 1.57 Å. In the second P site, P(2) is bonded to one O(5), one O(7), and two equivalent O(9) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-55°. The P(2)-O(5) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.56 Å. Both P(2)-O(9) bond lengths are 1.57 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one Li(1), and one C(2) atom to form distorted corner-sharing ONa2LiC tetrahedra. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(1), one Fe(1), and one C(1) atom. In the third O site, O(3) is bonded to one Na(3), two equivalent Na(1), one Fe(1), and one C(1) atom to form distorted ONa3FeC trigonal bipyramids that share  a cornercorner with one O(7)Na2FeP tetrahedra and corners with two equivalent O(1)Na2LiC tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Li(1), one Fe(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to two equivalent Na(1), one Fe(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Fe(2), and one P(1) atom. In the seventh O site, O(7) is bonded to two equivalent Na(2), one Fe(1), and one P(2) atom to form distorted corner-sharing ONa2FeP tetrahedra. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to two equivalent Na(2), one Fe(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Fe(2), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(2), one Fe(2), and one C(2) atom. In the eleventh O site, O(11) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one C(2) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to two equivalent Na(2), two equivalent Na(3), and one C(1) atom.